Flame-retardant epoxy resin composition, molded object thereof, and electronic part

ABSTRACT

The present invention has an object to provide a flame-retardant epoxy resin composition excellent in heat resistance and moisture resistance. A flame-retardant epoxy resin composition relating to the present invention contains an epoxy resin (A), a phosphazene compound (B), an epoxy hardener (C) and an inorganic filler (D), wherein the phosphazene compound (B) and the epoxy hardener (C) are included in the range of 0.01 to 70% by weight and in the range of 0 to 70% by weight, respectively, relative to a total quantity of the epoxy resin (A), the phosphazene compound (B) and the epoxy hardener (C), and the inorganic filler (D) is included in the range of 0 to 95% by weight relative to a total quantity of the epoxy resin (A), the phosphazene compound (B), the epoxy hardener (C) and the inorganic filler (D), wherein the phosphazene compound (B) is at least one selected from the group consisting of (1) a cyclic and/or a chain phosphazene compound with a specific structure, (2) a polymer of the cyclic and/or the chain phosphazene compound; and (3) a reaction product of the cyclic and/or the chain phosphazene compound with one type of a compound selected from the group consisting of an epoxy compound, a phenol compound, an amine compound and an acid anhydride.

TECHNICAL FIELD

[0001] The present invention relates to a flame-retardant epoxy resincomposition, a molded article thereof and an electronic part.

BACKGROUND ART

[0002] Epoxy resin has been widely used as insulating materials ofelectrical and electronic parts such as a laminate material and anencapsulating material for a semiconductor device, for example, IC, LSI,VLSI or the like because of excellencies in electrical characteristicssuch as insulating property, heat resistance, moisture resistance, acidresistance, solvent resistance, adhesiveness, mechanical properties,dimensional stability and others, and furthermore, relativeinexpensiveness.

[0003] In company with great development in the electronic technology inrecent years, a progress toward high integration in a semiconductordevice and a laminate has reached to higher level and at the same time,requirements for higher reliability thereof have been increased. In sucha current situation, epoxy resin used as an insulating material has alsobeen required to have better characteristics thereof such as heatresistance (including soldering heat resistance), a flame retardance,moisture resistance, adhesiveness and mechanical properties.

[0004] In order to improve characteristics, especially flame retardanceand heat resistance, of epoxy resin, a phosphazene compound iscompounded into the resin as a flame retardant and/or a hardener (forexample, Japanese Unexamined Patent Publication No. Sho-61-120850,Japanese Unexamined Patent Publication No. Sho-48-37500, JapaneseExamined Patent Publication No. Hei-3-4565, Japanese Examined PatentPublication No. Hei-6-104714 and Japanese Unexamined Patent PublicationNo. Hei-10-259292).

[0005] Phosphazene compounds disclosed in the prior arts all lack asufficient effect in an aspect of improving moisture resistance of epoxyresin. Moisture resistance of epoxy resin is an especially importantproperty in a case where the resin is used as material of a printedcircuit board. That is, since laminates have a chance to be used in theair with a high frequency and an insulating property and, hence, areliability are degraded due to moisture absorption, the resin isdesired to have a low water absorption and no change in electricalcharacteristics such as an insulating property. In a case where aphosphazene compound low in effect of improving moisture resistance isused as a laminate material, inconveniences such as swelling or peelingof a metal sheet, a metal foil or the like occurs due to moistureabsorption in a high temperature treatment such as a soldering process,thereby disabling a laminate with a long term reliability to beobtained.

DISCLOSURE OF THE INVENTION

[0006] The present inventors have conducted serious studies in order tosolve the above problem, which, as a result of the studies, leads to adiscovery that epoxy resin compounded with a specific phosphazenecompound can exert conspicuously excellent performance, thereby havingcompleted the present invention.

[0007] That is, according to the present invention, there is provided aflame-retardant epoxy resin composition containing an epoxy resin (A)and a phosphazene compound (B), wherein the component (B) is included inthe range of 0.01 to 70% by weight relative to a total quantity of thecomponent (A) and the component(B), and

[0008] wherein the component (B) is at least one member selected fromthe group consisting of

[0009] (1) a cyclic and/or a chain phosphazene compound expressed by ageneral formula

[0010] wherein each R¹ and R², being identical or different, is an alkylgroup having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylarylgroup having 7 to 18 carbon atoms, an alkenyl group having 2 to 18carbon atoms, an alkenylaryl group having 8 to 18 carbon atoms, an aminogroup-substituted phenyl group, an aminoalkyl group-substituted phenylgroup where the aminoalkyl group has 1 to 6 carbon atoms, a hydroxygroup-substituted phenyl group, a hydroxyalkyl group-substituted phenylgroup where the hydroxyalkyl group has 1 to 6 carbon atoms, aglycidyloxy group-substituted phenyl group or a glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms, providing that at least one of n R¹s and n R²s is theamino group-substituted phenyl group, the aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, thehydroxyalkyl group-substituted phenyl group where the hydroxyalkyl grouphas 1 to 6 carbon atoms, the glycidyloxy group-substituted phenyl groupor the glycidyloxyalkyl group-substituted phenyl group where theglycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates aninteger of from 3 to 10000;

[0011] (2) a polymer of the cyclic and/or the chain phosphazenecompound; and

[0012] (3) a reaction product of the cyclic and/or the chain phosphazenecompound with at least one compound selected from the group consistingof an epoxy compound, a phenol compound, an amine compound and an acidanhydride.

[0013] The flame-retardant epoxy resin composition is further compoundedwith an epoxy hardener (C), wherein the component (B) and the component(C) are included in the range of 0.01 to 70% by weight and in the rangeof 0 to 70% by weight, respectively, relative to a total quantity of thecomponent (A), the component(B) and the component (C).

[0014] Furthermore, according to the present invention, there isprovided a flame-retardant epoxy resin composition containing an epoxyresin (A), a phosphazene compound (B), an epoxy hardener (C) and aninorganic filler (D), wherein the component (B) and the component (C)are included in the range of 0.01 to 70% by weight and in the range of 0to 70% by weight, respectively, relative to a total quantity of thecomponent (A), the component(B) and the component (C), and the component(D) is included in the range of 0 to 95% by weight relative to a totalquantity of the component (A), the component(B), the component (C) andthe component (D) and

[0015] wherein the component (B) is at least one member selected fromthe group consisting of

[0016] (1) a cyclic and a chain phosphazene compound expressed by ageneral formula (1):

[0017] wherein each R¹ and R², being identical or different, is an alkylgroup having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylarylgroup having 7 to 18 carbon atoms, an alkenyl group having 2 to 18carbon atoms, an alkenylaryl group having 8 to 18 carbon atoms, an aminogroup-substituted phenyl group, an aminoalkyl group-substituted phenylgroup where the aminoalkyl group has 1 to 6 carbon atoms, a hydroxygroup-substituted phenyl group, a hydroxyalkyl group-substituted phenylgroup where the hydroxyalkyl group has 1 to 6 carbon atoms, aglycidyloxy group-substituted phenyl group or a glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms, providing that at least one of n R¹s and n R²s is theamino group-substituted phenyl group, the aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, thehydroxyalkyl group-substituted phenyl group where the hydroxyalkyl grouphas 1 to 6 carbon atoms, the glycidyloxy group-substituted phenyl groupor the glycidyloxyalkyl group-substituted phenyl group where theglycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates aninteger of from 3 to 10000;

[0018] (2) a polymer of the cyclic and/or the chain phosphazenecompound; and

[0019] (3) a reaction product of the cyclic and/or the chain phosphazenecompound with at least compound selected from the group consisting of anepoxy compound, a phenol compound, an amine compound and an acidanhydride.

[0020] A phosphazene compound of the component (B) used in the presentinvention is good in reactivity and compatibility with an epoxy resinand considered to act as a hardener and a flame retardant for the epoxyresin. This compound does not degrade electrical characteristics such asan insulating property, mechanical properties, adhesiveness and othersof the epoxy resin, rather exerts excellent performance to improve thecharacteristics and properties according to a case and, in addition,further increase moisture resistance. A high reliability is thereforeshown and also sustained over a long time by a molded article (a moldedproduct) obtained by molding a flame-retardant epoxy resin compositionof the present invention, for example an electronic part such as alaminate.

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] Description will be given for components used in the presentinvention below. Note that the term of a “polymer” used in thisspecification includes an oligomer.

[0022] Component (A): Epoxy Resins

[0023] As epoxy resins, there can be exemplified the following epoxyresins commonly used in the electrical and electronic fields: forexample, novolak epoxy resin obtained by a reaction between phenols andaldehydes, such as phenol novolak epoxy resin, brominated phenol novolakepoxy resin, orthocresol novolak epoxy resin or naphthol novolak epoxyresin; phenol epoxy resin obtained by a reaction between a phenol andepichlorohydrin, such as bisphenol-A epoxy resin, brominated bisphenol-Aepoxy resin, bisphenol-F epoxy resin, bisphenol-AD epoxy resin,bisphenol-S epoxy resin, biphenol epoxy resin, alkyl-substitutedbiphenol epoxy resin or tris(hydroxyphenyl) methane; aliphatic epoxyresin obtained by a reaction between an alcohol and epichlorohydrin,such as trimethylol propane, oligopropylene glycol or hydrogenatedbisphenol-A; glycidyl ester epoxy resin obtained by a reaction betweenhexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid andepichlorohydrin or 2-methyl epichlorohydrin; glycidyl amine epoxy resinobtained by a reaction between an amine such as diaminodiphenyl methaneor amino phenol and epichlorohydrin; heterocyclic epoxy resin obtainedby a reaction between a polyamine such as isocyanuric acid andepichlorohydrin; and modified compounds of the above epoxy resins. Amongthem, preferable are phenol novolak epoxy resin, orthocresol novolakepoxy resin, bisphenol-A epoxy resin, biphenol epoxy resin, phenol epoxyresin obtained by a reaction between tris(hydroxyphenyl) methane andepichlorohydrin and others. The epoxy resins can be used singly or in acombination of two or more thereof.

[0024] Component (B): Phosphazene Compounds

[0025] A phosphazene compound used as a component (B) of the presentinvention is at least one member selected from the group consisting of

[0026] (1) a cyclic and/or a chain phosphazene compound expressed by ageneral formula

[0027] wherein each R¹ and R², being identical or different, is an alkylgroup having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylarylgroup having 7 to 18 carbon atoms, an alkenyl group having 2 to 18carbon atoms, an alkenylaryl group having 8 to 18 carbon atoms, an aminogroup-substituted phenyl group, an aminoalkyl group-substituted phenylgroup where the aminoalkyl group has 1 to 6 carbon atoms, a hydroxygroup-substituted phenyl group, a hydroxyalkyl group-substituted phenylgroup where the hydroxyalkyl group has 1 to 6 carbon atoms, aglycidyloxy group-substituted phenyl group or a glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms, providing that at least one of n R¹s and n R²s isadditionally the amino group-substituted phenyl group, the aminoalkylgroup-substituted phenyl group where the aminoalkyl group has 1 to 6carbon atoms, the hydroxyalkyl group-substituted phenyl group where thehydroxyalkyl group has 1 to 6 carbon atoms, the glycidyloxygroup-substituted phenyl group or the glycidyloxyalkyl group-substitutedphenyl group where the glycidyloxyalkyl group has 4 to 9 carbon atoms,and n indicates an integer of from 3 to 10000;

[0028] (2) a phosphazene polymer obtained by polymerization of thecyclic and/or the chain phosphazene compound; and

[0029] (3) a reaction product of the cyclic and/or the chain phosphazenecompound with at least one compound selected from the group consistingof an epoxy compound, a phenol compound, an amine compound and an acidanhydride.

[0030] The phosphazene compounds can be used singly or in a combinationof two or more thereof.

[0031] The amino group-substituted phenyl group selectable as asubstituent indicated by R¹ and R² is a group obtained by substituting 1to 5 amino and/or aminoalkyl groups at any carbon atom or atoms on abenzene ring. This applies to the aminoalkyl group-substituted phenylgroup where the aminoalkyl group has 1 to 6 carbon atoms, the hydroxygroup-substituted phenyl group, the hydroxyalkyl group-substitutedphenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, theglycidyloxy group-substituted phenyl group and the glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms in a similar manner.

[0032] Note that an alkali metal salt described hereinafter means apotassium salt, a sodium salt, a lithium salt or the like.

[0033] Amino Phosphazene Compound (1a)

[0034] An amino phosphazene compound (1a) that is a phosphazene compound(1) in which at least one of n R¹s and n R²s is additionally an aminogroup-substituted phenyl group and/or an aminoalkyl group-substitutedphenyl group is obtained according to a known prior method, for example,in which an alkali metal salt of nitrophenol and/or nitroalkyl phenoland phosphonitrile chloride are reacted with each other to producenitrophenoxy phosphazene or nitroalkylphenoxy phosphazene and then,hydrazine or hydrazine hydrate is used to reduce a nitro group thereofto an amino group in the presence of a catalyst with a halide of a metalselected from the group consisting of chromium, manganese, iron, cobalt,nickel, zinc and tin, or a sulfate carried on active charcoal.Furthermore, there can be adopted a catalytic hydrogenation method usinga Raney nickel catalyst described in Inorganic Chemistry, 6(2), 394,1967 and a known lithium aluminum hydride reduction method or a knownboron hydride reduction method.

[0035] Furthermore, in the reaction of an alkali metal salt ofnitrophenol and/or nitroalkyl phenol and phosphonitrile chloride witheach other, there can be included, as a reactant, at least one selectedfrom the group consisting of alcohol compounds expressed by R³OM (in theformula, R³ indicates an alkyl group having 1 to 18 carbon atoms, acycloalkyl group having 5 to 8 carbon atoms, an alkylaryl group having 7to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms; andM indicates lithium, sodium or potassium) and phenol compounds expressedby R⁴OM (in the formula, R⁴ indicates an aryl group having 6 to 14carbon atoms or an alkenylaryl group having 8 to 18 carbon atoms and Mindicates lithium, sodium or potassium). Thereby, there are obtainedaminophosphazene compounds (1a) each having plural amino and/oraminoalkyl group-substituted phenol groups as substitutes.

[0036] As nitrophenols and nitroalkyl phenols, there are named, forexample, 3-nitrophenol, 4-nitrophenol, 4-nitromethyl phenol,4-nitroethyl phenol, 4-nitrobutyl phenol and others.

[0037] As alcohol compounds and phenol compounds, there are named, forexample, alkali metal salts of methanol, ethanol, n-propanol,allylalcohol, isopropanol, n-butanol, n-octanol, 2,2,2-trifluoroethanol,2,2,3,3,4,4,5,5-octafluoropentyl alcohol, phenol, 4-methyl phenol,4-ethyl phenol, 1-naphtol, 2-natphthol, 4-allyl phenol, 4-chlorophenol,4-trifluoromethyl phenol and others and sodium phenolate or sodium4-methyl phenolate is preferable in terms of heat resistance.

[0038] As concrete examples of aminophosphazene compounds (1a), therecan be named, for example, cyclotriphosphazenes with an aminophenoxygroup and a phenoxy group as substitutes in a mixed manner such asaminophenoxy-pentaphenoxycyclotriphosphazene,di(aminophenoxy)-tetraphenoxycyclotriphosphazene,tri(aminophenoxy)-triphenoxycyclotriphosphazene,tetra(aminophenoxy)-diphenoxycyclotriphosphazene,penta(aminophenoxy)-phenoxycyclotriphosphazene, andhexaaminophenoxycyclotriphosphazene; cyclotriphosphazenes with anaminomethylphenoxy group and a phenoxy group as substitutes in a mixedmanner such as aminomethylphenoxy-pentaphenoxycyclotriphosphazene,di(aminomethylphenoxy)-tetraphenoxycyclotriphosphazene,tri(aminomethylphenoxy)-triphenoxycyclotriphosphazene,tetra(aminomethylphenoxy)-diphenoxycyclotriphosphazene,penta(aminomethylphenoxy)-phenoxycyclotriphosphazene, andhexaaminomethylphenoxy cyclotriphosphazene; cyclotriphosphazenes with anaminoethylphenoxy group and a phenoxy group as substitutes in a mixedmanner such as aminoethylphenoxy-pentaphenoxycyclotriphosphazene,di(aminoethylphenoxy)-tetraphenoxycyclotriphosphazene,tri(aminoethylphenoxy)-triphenoxycyclotriphosphazene,tetra(aminoethylphenoxy)-diphenoxycyclotriphosphazene,penta(aminoethylphenoxy)-phenoxycyclotriphosphazene, andhexaaminoethylphenoxy cyclotriphosphazene; cyclotriphosphazenes with anaminobutylphenoxy group and a phenoxy group as substitutes in a mixedmanner such as aminobutylphenoxy-pentaphenoxycyclotriphosphazene,di(aminobutylphenoxy)-tetraphenoxycyclotriphosphazene,tri(aminobutylphenoxy)-triphenoxycyclotriphosphazene,tetra(aminobutylphenoxy)-diphenoxycyclotriphosphazene,penta(aminobutylphenoxy)-phenoxycyclotriphosphazene, andhexaaminobutylphenoxy-cyclotriphosphazene; and others.

[0039] Furthermore, there are named cyclotriphosphazenes with anaminoethylphenoxy group, and an octyloxy group, trifluoroethoxy group,an octafluoropentyloxy group, an ethylphenoxy group, a naphthyloxygroup, an allyloxy group, a chlorophenoxy group or atrifluoromethylphenoxy group as substitutes in a mixed manner.

[0040] Furthermore, there are named cyclotetraphosphazene,cyclopentaphosphazene, cyclohexaphosphazene, a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n being 3000 on average) and a cyclic(=cyclo) and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n=1000 on average) eachwith an aminophenoxy group and a phenoxy group as substitutes in a mixedmanner.

[0041] Furthermore, there are named cyclotetraphosphazene,cyclopentaphosphazene, cyclohexaphosphazene, a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n=3000 on average) and a cyclic (=cyclo)and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n=1000 on average) eachwith an aminoethylphenoxy group and a phenoxy group as substitutes in amixed manner. The aminophosphazene compounds may include mixtures ofcompounds with two or more types of substituents.

[0042] Among the above aminophosphazenes (1a), preferable are, forexample, hexaaminophenoxycyclotriphosphazene;hexaaminoethylphenoxycyclotriphosphazene; a cyclotriphosphazene with anaminophenoxy group and a phenoxy group as substitutes in a mixed manner;a cyclotriphosphazene with an aminoethylphenoxy group and a phenoxygroup as substitutes in a mixed manner; a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with an aminophenoxy group and a phenoxy group as substitutes ina mixed manner; a linear phosphazene mixture (a mixture of linearphosphazenes of the general formula (1) with n=3000 on average) with anaminoethylphenoxy group and a phenoxy group as substitutes in a mixedmanner and especially preferable are a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with an aminophenoxy group and a phenoxy group as substitutes ina mixed manner and a linear phosphazene mixture (a mixture of linearphosphazenes of the general formula (1) with n=3000 on average) with anaminoethylphenoxy group and a phenoxy group as substitutes in a mixedmanner.

[0043] Hydroxy Phosphazene Compound (1b)

[0044] A hydroxy phosphazene compound (1b) that is a phosphazenecompound (1) in which at least one of n R¹s and n R²s is additionally ahydroxy group-substituted phenyl group and/or a hydroxyalkylgroup-substituted phenyl group can be obtained according to knownmethods described in articles and a patent publication; for example,Masaaki YOKOYAMA, et.al.,; Journal of the Chemical Society of Japan.Industrial chemistry, Vol. 67, No. 9, p. 1378 (1964), Tomoya OKUBASHI,et.al.,; Journal of the Chemical Society of Japan. Industrial chemistry,Vol. 73, No. 6, p. 1164 (1970), Japanese Unexamined Patent PublicationNo. Sho-58-219190, Alessandro Medici, et. al., Macromolecules, Vol. 25,No. 10, p. 2569 (1992) and others. That is, an alkali metal salt of4-methoxyphenol or 4-(benzyloxy)phenol in which one hydroxyl group ofbivalent phenol is protected by a methyl group or benzyl group andphosphonitrile chloride (Japanese Unexamined Patent Publication No.Sho-54-145394, Japanese Unexamined Patent Publication No. Sho-54-145395and others) are reacted with each other and thereafter, a reaction withpyridine hydrogen halide salt or boron trifluoride is performed tochange a methyl group or a benzyl group serving as deprotection to ahydroxyl group, thus enabling production of hydroxyphenoxy phosphazene.

[0045] Furthermore, a hydroxy phosphazene compound (1b) can also beproduced by a reaction of an alkali meal salt of a hydroxyalkyl phenolsuch as 2-hydroxymethyl phenol, 3-hydroxymethyl phenol, 4-hydroxymethylphenol, 4-hydroxyethyl phenol and 4-hydroxybutyl phenol withphosphonitrile chloride.

[0046] A hydroxy phosphazene compound (1b) in which plural ones of n R¹sand n R²s are hydroxy groups and/or hydroxyalkyl groups is produced onlyby using at least one selected from the group consisting of alcoholcompounds expressed by a formula of R³OM (in the formula, R³ and M arethe same as those of an aminophosphazene compound (1a) described above)and phenol compounds expressed by a formula of R⁴OM (in the formula, R⁴and M are the same as those of an aminophosphazene compound (1a)described above) together in a reaction between an alkali metal salt of4-methoxyphenol, or 4-(benzyloxy)phenol in which one hydroxyl group ofdihydric phenol is protected by a methyl group or benzyl group and/or analkali metal salt of a hydroxyalkyl phenol described above, andphosphonitrile chloride.

[0047] As examples of compounds in which one hydroxyl group of dihydricphenol is protected by a methyl group or benzyl group, there are named4-methoxyphenol, 3-methoxyphenol, 2-methoxyphenol, 4-(benzyloxy)phenoland others.

[0048] In order to obtain a compound in which all of chlorine atoms ofphosphonitrile chloride are substituted with methoxyphenoxy and/or4-(benzyloxy)phenoxy, a phosphonitrile chloride solution is added to asolution of an alkali metal salt of methoxyphenol or 4-(benzyloxy)phenolto cause a reaction therebetween. This reaction is preferably performedin an organic solvent such as benzene, toluene, xylene, ether,tetrahydrofuran or the like at room temperature for a time of from 1 to20 hours, followed by the reaction at a reflux temperature of a solventin use for a time of about 1 to 3 hours for completion thereof. On theother hand, in order to obtain a compound in which part of chlorineatoms of phosphonitrile chloride is substituted with a methoxyphenoxygroup and/or a benzylphenoxy group, a solution of an alkali metal saltof methoxyphenol or 4-(benzyloxy)phenol prepared quantitatively so as toleave the other part of chlorine atoms of phosphonitrile chlorideunsubstituted during the reaction is added to a phosphonitrile chloridesolution with a preferable result. By substituting unsubstitutedchlorine atoms of partially substituted phosphonitrile chloride with analkali metal salt of an alcohol or phenol compound described above,there can be obtained a compound with a methoxyphenoxy or4-(benzyloxy)phenoxy group and R³O-group and/or R⁴O-group (R³ and R⁴ arethe same as those in an aminophosphazene compound (1a) described above)as substitutes in a mixed manner. The reaction is preferably caused inconditions of a temperature from room temperature to a refluxtemperature or lower of a solvent in use and a time ranging about 3 toabout 8 hours. Note that, in this case, a method can be adopted in whicha mixed solution of an alkali metal salt of methoxyphenol or4-(benzyloxy)phenol and an alkali metal salt of alcohol or phenolcompound is prepared in advance and a phosphonitrile halide solution isadded dropwise to the mixed solution to cause a reaction with a similareffect. Then, a removal reaction of a methyl or a benzyl protectivegroup as a substitute of a methoxyphenoxy group or a benzyloxy group asa substitute is preferably performed in a way that pyridine hydrogenhalide salt of a quantity in equivalent about 2 to 20 times, orpreferably about 5 to 10 times as large as one equivalent quantity of amethyl or a benzyl protective group is used to cause a reaction at areflux temperature for about 1 hour or less, while with more than areaction time of 1 hour, a reaction product decomposes to reduce ayield. As pyridine hydrogen halide salts, there are named pyridinehydrogen chloride salt, pyridine hydrogen bromide salt and others.Removal of a methyl or a benzyl group as a protective group can also beachieved using a reagent such as iodotrimethylsilane, aluminumtrichloride, aluminum tribromide, boron trifluoride, boron tribromide,hydrogen bromide, hydrogen iodide and others.

[0049] Furthermore, in order to obtain a compound in which all ofchlorine atoms of phosphonitrile chloride are substituted with ahydroxyalkylphenoxy group (for example, a hydroxymethylphenoxy group, ahydroxyethylphenoxy group, a hydroxybutylphenoxy group or the like), thecompound can be produced in a way that 1.01 to 2.0 equivalents of analkali metal salt of a hydroxyalkyl phenol is used relative to chlorineof phosphonitrile chloride to cause a reaction preferably in an organicsolvent such as benzene, toluene, xylene, ether, tetrahydrofuran or thelike at room temperature for a time ranging 1 to 20 hours, followed bythe reaction at a reflux temperature of a solvent in use for a timeranging from about 1 to about 3 hours to complete the reaction.

[0050] In order to obtain a compound in which part of chlorine atoms ofphosphonitrile chlorides substituted with a hydroxyalkylphenoxy group, asolution of an alkali metal salt of hydroxyalkylphenol prepared so as toleave the other part of chlorine atoms of phosphonitrile chlorideunsubstituted during the reaction is added to a phosphonitrile halidesolution with a preferable result. By substituting unsubstitutedchlorine atoms of partially substituted phosphonitrile chloride with analkali metal salt of an alcohol or phenol compound described above,there can be obtained a compound with a hydroxyalkylphenoxy group andR³O-group and/or R⁴O-group (R³ and R⁴ are the same as those in anaminophosphazene compound (1a) described above) as substitutes in amixed manner. A reaction is preferably caused in conditions of atemperature from room temperature to a reflux temperature or lower of asolvent in use and a time ranging about 3 to about 8 hours. Note that,in this case, a method can be adopted in which a mixed solution of analkali metal salt of hydroxyalkylphenol and an alkali metal salt ofalcohol or phenol compound is prepared in advance and a phosphonitrilehalide solution is dropwise added to the mixed solution to cause areaction with a similar effect.

[0051] As concrete examples of hydroxyphosphazene compounds (1b), therecan be named, for example, cyclotriphosphazenes with a hydroxyphenoxygroup and a phenoxy group as substitutes in a mixed manner such ashydroxyphenoxy-pentaphenoxycyclotriphosphazene,di(hydroxyphenoxy)-tetraphenoxycyclotriphosphazene,tri(hydroxyphenoxy)-triphenoxycyclotriphosphazene,tetra(hydroxyphenoxy)-diphenoxycyclotriphosphazene,penta(hydroxyphenoxy)-phenoxycyclotriphosphazene, and hexahydroxyphenoxycyclotriphosphazene; cyclotriphosphazenes with a hydroxymethylphenoxygroup and a phenoxy group as substitutes in a mixed manner such ashydroxymethylphenoxy-pentaphenoxycyclotriphosphazene,di(hydroxymethylphenoxy)-tetraphenoxycyclotriphosphazene,tri(hydroxymethylphenoxy)-triphenoxycyclotriphosphazene,tetra(hydroxymethylphenoxy)-diphenoxycyclotriphosphazene,penta(hydroxymethylphenoxy)-phenoxycyclotriphosphazene, andhexahydroxymethylphenoxy cyclotriphosphazenes; cyclotriphosphazenes witha hydroxyethylphenoxy group and a phenoxy group as substitutes in amixed manner such ashydroxyethylphenoxy-pentaphenoxycyclotriphosphazene,di(hydroxyethylphenoxy)-tetraphenoxycyclotriphosphazene,tri(hydroxyethylphenoxy)-triphenoxycyclotriphosphazene,tetra(hydroxyethylphenoxy)-diphenoxycyclotriphosphazene,penta(hydroxyethylphenoxy)-phenoxycyclotriphosphazene, andhexahydroxyethylphenoxy cyclotriphosphazenes; cyclotriphosphazenes witha hydroxybutylphenoxy group and a phenoxy group as substitutes in amixed manner such ashydroxybutylphenoxy-pentaphenoxycyclotriphosphazene,di(hydroxybutylphenoxy)-tetraphenoxycyclotriphosphazene,tri(hydroxybutylphenoxy)-triphenoxycyclotriphosphazene,tetra(hydroxybutylphenoxy)-diphenoxycyclotriphosphazene,penta(hydroxybutylphenoxy)-phenoxy cyclotriphosphazene, andhexahydroxybutylphenoxy cyclotriphosphazenes.

[0052] Furthermore, there are named cyclotriphosphazenes with ahydroxyethylphenoxy group, and a butoxy group, an octyloxy group,trifluoroethoxy group, an octafluoropentyloxy group, an ethylphenoxygroup, a naphthyloxy group, an allyloxy group, an allylphenoxy group, achlorophenoxy group or a trifluoromethylphenoxy group as substitutes ina mixed manner.

[0053] Furthermore, there are named cyclotetraphosphazene,cyclopentaphosphazene, cyclohexaphosphazene, a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n=3000 on average) and a cyclic (=cyclo)and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n=1000 on average) eachwith a hydroxyphenoxy group and a phenoxy group as substitutes in amixed manner.

[0054] Furthermore, there are named cyclotetraphosphazene,cyclopentaphosphazene, cyclohexaphosphazene, a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n=3000 on average) and a cyclic (=cyclo)and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n=1000 on average) eachwith a hydroxyethylphenoxy group and a phenoxy group as substitutes in amixed manner. The hydroxyphosphazene compounds may include mixtures ofcompounds with two or more types of substituents.

[0055] Among the above hydroxyphosphazenes, preferable are, for example,hexahydroxyphenoxycyclotriphosphazene;hexahydroxyethylphenoxycyclotriphosphazene; a cyclotriphosphazene with ahydroxyphenoxy group, a hydroxyethylphenoxy group and a phenoxy group assubstitutes in a mixed manner; a cyclophosphazene mixture (a mixture ofcyclophosphazenes of the general formula (1) with n being 3 to 15) witha hydroxyphenoxy group and a phenoxy group as substitutes in a mixedmanner; a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n=3000 on average) with ahydroxyethylphenoxy group and a phenoxy group as substitutes in a mixedmanner, and especially preferable are a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with a hydroxyphenoxy group and a phenoxy group as substitutes ina mixed manner and a linear phosphazene mixture (a mixture of linearphosphazenes of the general formula (1) with n=3000 on average) with ahydroxyethylphenoxy group and a phenoxy group as substitutes in a mixedmanner.

[0056] Glycidylphosphazene Compound (1c)

[0057] A glycidyl phosphazene compound (1c) can be produced in a waythat a hydroxyphosphazene compound (1b) and epihalohydrin are reactedwith each other in a solvent-free condition or in a proper solvent suchas dimethyl sulfoxide in the presence of a quaternary ammonium salt suchas tetramethyl ammonium chloride, tetramethyl ammonium bromide or thelike, an alkali metal hydroxide such as sodium hydroxide, potassiumhydroxide or the like. In a case where a quaternary ammonium salt isused, since a reaction is ceased at a stage of a ring opening additionreaction, the above reaction is followed by addition of an alkali metalhydroxide to cause an ring closing reaction. If an alkali metalhydroxide is added at the start of the reaction, the ring openingaddition reaction and the ring closing reaction can be performedsuccessively.

[0058] As epihalohydrins, there can be used known compounds and thefollowing are named: epichlorohydrin, epibromohydrin, epiiodohydrin andothers. A quantity of usage thereof is generally in the range of from 1to 50 mol and preferably in the range of from 3 to 15 mol per 1 mol ofhydroxyl group of hydroxyphosphazene compound (1b).

[0059] In a case where dimethyl sulfoxide is used, a quantity of usagethereof has only to be in the range of from 20 to 200 parts by weightrelative to 100 parts by weight of epihalohydrin.

[0060] A quantity of usage of an alkali metal hydroxide has only to begenerally in the range of from 0.8 to 1.5 mol and preferably in therange of from 0.9 to 1.3 mol per 1 mol of hydroxyl group of ahydroxyphosphazene compound (1b). A quantity of usage of a quaternaryammonium salt has only to be generally in the range of 0.001 to 1 moland preferably in the range of 0.005 to 0.5 mol per 1 mol of a hydroxylgroup of a hydroxyphosphazene compound (1b).

[0061] The reaction temperature is generally set in the range of from 20to 130° C. and preferably in the range of from 30 to 100° C. Thereaction can also be progressed while water produced during the reactionis removed to outside the reaction system. After the reaction ends, asalt, dimethyl sulfoxide, and others as byproducts are removed bywashing with water and epihalohydrin in excess is removed as adistillate, thereby enabling a glycidyl phosphazene compound (1c).

[0062] In order to remove an impurity, the obtained glycidyl phosphazenecompound (1c) may be dissolved into a solvent such as methylisobutylketone or the like to then, cause the solution to be heated at atemperature in the range of from 50 to 100° C. for a time in the rangeof from 0.5 to 3 hours in the presence of an alkali metal hydroxide suchas sodium hydroxide or the like. After the heat treatment, the solutionis repeatedly washed with water to cause a water phase to be neutral anda solvent such as methylisobutyl ketone or the like is removed as adistillate under a reduced pressure, thereby obtaining a glycidylphosphazene compound (1c) with an extremely high purity. In thisprocess, a quantity of usage of an alkali metal hydroxide is in therange of from 0.01 to 0.2 mol per 1 mol of an epoxy group of theglycidyl phosphazene compound (1c) to be processed. By repeating such aprocess, there can be obtained a glycidyl phosphazene compound (1c) witha much higher purity.

[0063] As concrete examples of glycidyl phosphazene compounds (1b),there are named the following compounds, for example,cyclotriphosphazenes with a glycidyloxyphenoxy group and a phenoxy groupas substitutes in a mixed manner such asglycidyloxyphenoxy-pentaphenoxycyclotriphosphazene,di(glycidyloxyphenoxy)-tetraphenoxycyclotriphosphazene,tri(glycidyloxyphenoxy)-triphenoxycyclotriphosphazene,tetra(glycidyloxyphenoxy)-diphenoxycyclotriphosphazene,penta(glycidyloxyphenoxy)-phenoxycyclotriphosphazene, andhexaglycidyloxyphenoxy cyclotriphosphazenes; cyclotriphosphazenes with aglycidyloxymethylphenoxy group and a phenoxy group as substitutes in amixed manner such asglycidyloxymethylphenoxy-pentaphenoxycyclotriphosphazene,di(glycidyloxymethylphenoxy)-tetraphenoxy cyclotriphosphazene,tri(glycidyloxymethylphenoxy)-triphenoxycyclotriphosphazene,tetra(glycidyloxymethylphenoxy)-diphenoxy-cyclotriphosphazene,penta(glycidyloxymethylphenoxy)-phenoxycyclotriphosphazene, andhexaglycidyloxymethylphenoxy cyclotriphosphazenes; cyclotriphosphazeneswith a glycidyloxyethylphenoxy group and a phenoxy group as substitutesin a mixed manner such asglycidyloxyethylphenoxy-pentaphenoxycyclotriphosphazene,di(glycidyloxyethylphenoxy)-tetraphenoxy-cyclotriphosphazene,tri(glycidyloxyethylphenoxy)-triphenoxy cyclotriphosphazene,tetra(glycidyloxyethylphenoxy)-diphenoxy-cyclotriphosphazene,penta(glycidyloxyethylphenoxy)-phenoxy cyclotriphosphazene, andhexaglycidyloxyethylphenoxycyclotriphosphazenes; cyclotriphosphazeneswith a glycidyloxybutylphenoxy group and a phenoxy group as substitutesin a mixed manner such asglycidyloxybutylphenoxy-pentaphenoxycyclotriphosphazene,di(glycidyloxybutylphenoxy)-tetraphenoxy cyclotriphosphazene,tri(glycidyloxybutylphenoxy)-triphenoxycyclotriphosphazene,tetra(glycidyloxybutylphenoxy)-diphenoxy cyclotriphosphazene,penta(glycidyloxybutylphenoxy)-phenoxy cyclotriphosphazene, andhexaglycidyloxybutylphenoxycyclotriphosphazenes.

[0064] Furthermore, there are named cyclotriphosphazenes with aglycidyloxyethylphenoxy group, and a butoxy group, an octyloxy group, atrifluoroethoxy group, an octafluoropentyloxy group, an ethylphenoxygroup, a naphthyloxy group, an allyloxy group, an allylphenoxy group, achlorophenoxy group, a trifluoromethylphenoxy group or the like assubstitutes in a mixed manner.

[0065] Furthermore, there are named cyclotetraphosphazene,cyclopentaphosphazene, cyclohexaphosphazene, a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenesof the general formula (1) with n=3000 on average) and a cyclic (=cyclo)and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n=1000 on average) eachwith a glycidyloxyphenoxy group and a phenoxy group as substitutes in amixed manner.

[0066] Furthermore, there are named cyclohexaphosphazene with aglycidyloxyethylphenoxy group, a glycidyloxyethylphenoxy group, aglycidyloxyethylphenoxy group or the like,and a phenoxy group in a mixedmanner, a cyclophosphazene mixture (a mixture of cyclophosphazenes ofthe general formula (1) with n being 3 to 15) with aglycidyloxyethylphenoxy group and a phenoxy group as substitutes in amixed manner, a linear phosphazene mixture (a mixture of linearphosphazenes of the general formula (1) with n=3000 on average) with aglycidyloxyethylphenoxy group and a phenoxy group as substitutes in amixed manner, and a cyclic (=cyclo) and linear phosphazene mixture (amixture of cyclic and linear phosphazenes of the general formula (1)with n=1000 on average) each with a glycidyloxyethylphenoxy group and aphenoxy group as substitutes in a mixed manner. The glycidyl phosphazenecompounds may include mixtures of compounds with two or more types ofsubstituents.

[0067] Among the above glycidyl phosphazene compounds, preferable are,for example, hexaglycidyloxyphenoxy cyclotriphosphazene;hexaglycidyloxyethylphenoxy cyclotriphosphazene; cyclotriphosphazenewith a glycidyloxyphenoxy group and a phenoxy group as substitutes in amixed manner; cyclotriphosphazene with a glycidyloxyethylphenoxy groupand a phenoxy group as substitutes in a mixed manner; a cyclophosphazenemixture (a mixture of cyclophosphazenes of the general formula (1) withn being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner; a linear phosphazene mixture (a mixtureof linear phosphazenes of the general formula (1) with n=3000 onaverage) with a glycidyloxyethylphenoxy group and a phenoxy group assubstitutes in a mixed manner, and especially preferable are acyclophosphazene mixture (a mixture of cyclophosphazenes of the generalformula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and aphenoxy group as substitutes in a mixed manner and a linear phosphazenemixture (a mixture of linear phosphazenes of the general formula (1)with n=3000 on average) with a glycidyloxyethylphenoxy group and aphenoxy group as substitutes in a mixed manner.

[0068] Polymer of Phosphazene Compound (1)

[0069] As polymers of a phosphazene compound (1), there are named, forexample, polymers obtained by polymerization of one type or two or moretypes of grycidylphosphazene compounds (1c).

[0070] Polymer of Grycidylphosphazene Compound (1c)

[0071] A polymer of a glycidyl phosphazene compound (1c) is generallyobtained by polymerizing a glycidyl phosphazene compound (1c) whileheating in a solvent-free condition or in an organic solvent, in thepresence of a catalyst such as a Lewis acid including aluminum chloride,boron trifluoride, iron chloride and antimony chloride, an alkali metalhydroxide including sodium hydroxide and potassium hydroxide, an organicaluminum compound including triethyl aluminum and aluminum tributoxideand an organic zinc compound including diethyl zinc and others or in theabsence thereof In a case where hexaglycidyloxyphenoxycyclotriphosphazene is used, for example, a reaction is caused in anorganic solvent such as benzene, toluene, xylene, ether ortetrahydrofuran in the presence of potassium hydroxide as a catalyst ata temperature in the range of from 50° C. to a reflux temperature of asolvent in use for a time in the range of from 1 to 20 hours andthereafter, the solvent and the catalyst used in the reaction areremoved through operations such as concentration, washing and others,thereby obtaining the target compound.

[0072] As concrete examples of polymers of a glycidyl phosphazenecompound (1c), there are named the following polymers, for example,oligo or poly(glycidyloxyphenoxy-pentaphenoxy cyclotriphosphazene),oligo or poly(tri(glycidyloxyphenoxy)-triphenoxycyclotriphosphazene),oligo or poly(hexaglycidyloxyphenoxy-cyclotriphosphazene); oligo orpoly(glycidyloxyethylphenoxy-pentaphenoxy cyclotriphosphazene), oligo orpoly(tri(glycidyloxyethylphenoxy)-triphenoxy cyclotriphosphazene), oligoor poly(hexaglycidyloxyethylphenoxycyclotriphosphazene), a polymer of acyclophosphazene mixture (a mixture of cyclophosphazenes of the generalformula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and aphenoxy group as substitutes in a mixed manner, a polymer of acyclophosphazene mixture (a mixture of cyclophosphazenes of the generalformula (1) with n being 3 to 15) with a glycidyloxyethylphenoxy groupand a phenoxy group as substitutes in a mixed manner, a polymer of acyclic (=cyclo) and linear phosphazene mixture (a mixture of cyclic andlinear phosphazenes of the general formula (1) with n being 1000 onaverage) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner and, and a polymer of a cyclic (=cyclo)and linear phosphazene mixture (a mixture of cyclic and linearphosphazenes of the general formula (1) with n being 1000 on average)with a glycidyloxyethylphenoxy group and a phenoxy group. as substitutesin a mixed manner.

[0073] Among the polymers, preferable are oligo orpoly(glycidyloxyphenoxy-pentaphenoxycyclotriphosphazene), oligo orpoly(glycidyloxyethylphenoxy-pentaphenoxy-cyclotriphosphazene), apolymer of a cyclophosphazene mixture (a mixture of cyclophosphazenes ofthe general formula (1) with n being 3 to 15) with a glycidyloxyphenoxygroup and a phenoxy group as substitutes in a mixed manner, a polymer ofa cyclophosphazene mixture (a mixture of cyclophosphazenes of thegeneral formula (1) with n being 3 to 15) with a glycidyloxyethylphenoxygroup and a phenoxy group as substitutes in a mixed manner, andespecially preferable are a polymer of a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner, a polymer of a cyclophosphazene mixture(a mixture of cyclophosphazenes of the general formula (1) with n being3 to 15) with a glycidyloxyethylphenoxy group and a phenoxy group assubstitutes in a mixed manner and others.

[0074] Reaction Compound between Phosphazene Compound (1) and OtherCompounds

[0075] As reaction compounds of a phosphazene compound (1) with at leastone type of compound selected from the group consisting of an epoxycompound, a phenol compound, an amine compound and an acid anhydride(the compounds are hereinafter referred collectively to as a reactivegroup containing compound unless otherwise specified), there are namedthe following copolymers, for example, a copolymer obtained bypolymerizing an aminophosphazene compound (1a) and/or ahydroxyphosphazene compound (1b) with an epoxy compound, a copolymerobtained by polymerizing a glycidylphosphazene compound (1c) with areactive group containing compound and others.

[0076] Copolymer of Aminophophazene Compound (1a) and/orHydroxyphosphazene Compound (1b) with Epoxy Compound

[0077] Copolymerization of an aminophosphazene compound (1a) and/or ahydroxyphosphazene compound (1b) with an epoxy compound is performed,for example, by heating in an organic solvent or in a solvent-freecondition in the presence or absence of a curing catalyst. In a casewhere hexaaminophenoxy cyclotriphosphazene or hexahydroxyphenoxycyclotriphosphazene reacts with diglycidyl ether of bisphenol A, forexample, a reaction has only to be caused in an organic solvent such asbenzene, toluene, xylene, ether, tetrahydrofuran or the like usingpotassium hydroxide as a curing catalyst at a temperature in the rangeof from 50° C. to a reflux temperature of a used solvent for a time inthe range of from 1 to 20 hours and after the reaction ends, the solventand the used catalyst are removed by operations such as concentration,washing and others, thereby enabling a desired copolymer to be obtained.

[0078] As epoxy compounds, there can be used an epoxy resin and amonomer for an epoxy resin. Epoxy resins can be the same as the knownepoxy resins described above. Known monomers can be used as a monomerfor epoxy resin and there can be named, for example, bifunctional epoxycompounds such as ethylene glycol diglycidyl ether, propylene glycoldiglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanedioldiglycidyl ether, diglycidyl ether of bisphenol A, butadiene diepoxide,3, 4-epoxycyclohexylmethyl-(3, 4-epoxy)cyclohexane carboxylate,vinylcyclohexane dioxide, 4,4′,-di(1,2-epoxyethyl)diphenyl ether,4,4′-(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane,glycidyl ether of resorcinol, diglycidyl ether of phloroglucin,diglycidyl ether of methyl phloroglucin, bis(2,3-epoxycyclopentyl)ether, 2(3, 4-epoxy)cyclohexane-5,5spiro(3,4-epoxy)cyclohexane-m-dioxane, bis(3,4epoxy-6-methylcyclohexyl)adipate,N,N′-m-phenylenebis(4,5-epoxy-1,2cyclohexane)dicarboxyimide; tri- orhigher functional epoxy compounds such triglycidyl ether ofp-aminophenol, polyallyl glycidyl ether, 1,3, 5-tri(1,2-epoxyethyl)benzene, 2,2′,4,4′-tetraglycidoxybenzophenone, polyglycidylether of phenol formaldehyde novolak, triglycidyl ether oftrimethylolpropane and others. Epoxy resins and monomers thereof areused singly or in a combination of two or more thereof.

[0079] As concrete examples of copolymers between an aminophosphazenecompounds (1a) and an epoxy compound, there are named the followingcopolymers, for example, between epoxy compounds such as diglycidylether of bisphenol A, 4,4′-(1,2-epoxyethyl)biphenyl,2,2bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol,diglycidyl ether of fluoroglucin or the like; and hexaaminophenoxycyclotriphosphazene, hexaaminoethylphenoxy cyclotriphosphazene, acyclotriphospazene with an aminophenoxy group and a phenoxy group assubstitutes in a mixed manner, a cyclotriphospazene with anaminoethylphenoxy group and a phenoxy group as substitutes in a mixedmanner, a cyclophosphazene mixture (a mixture of cyclophosphazenes ofthe general formula (1) with n being 3 to 15) with an aminophenoxy groupand a phenoxy group as substitutes in a mixed manner, a linearphosphazene mixture (a mixture of linear phosphazenes of the generalformula (1) with n=3000 on average) with an aminoethylphenoxy group anda phenoxy group as substitutes in a mixed manner or the like. Thecopolymers can be used singly or in a combination of two or morethereof. In a reaction between an aminophosphazene compound (1a) and anepoxy compound, a terminal end of a copolymer produced from the reactionmay be an amino group or an epoxy group according to a quantitativerelation therebetween.

[0080] As concrete examples of copolymers between a hydroxyphosphazenecompounds (1b) and an epoxy compound, there are named the followingcopolymers, for example, between hexahydroxyphenoxy cyclotriphosphazene,hexahydroxyethylphenoxy cyclotriphosphazene, a cyclotriphospazene with ahydroxyphenoxy group and a phenoxy group as substitutes in a mixedmanner, a cyclotriphosphazene with a hydroxyethylphenoxy group and aphenoxy group as substitutes in a mixed manner, a cyclophosphazenemixture (a mixture of cyclophosphazenes of the general formula (1) withn being 3 to 15) with a hydroxyphenoxy group and a phenoxy group assubstitutes in a mixed manner, a linear phosphazene mixture (a mixtureof linear phosphazenes of the general formula (1) with n being 3000 onaverage) with a hydroxyphenoxy group and a phenoxy group as substitutesin a mixed manner or the like; and diglycidyl ether of bisphenol A,4,4′-(1,2-epoxyethyl)biphenyl, 2, 2bis(3, 4-epoxycyclohexyl)propane,glycidyl ether of resorcinol, diglycidyl ether of phloroglucin or thelike. The copolymers can be used singly or in a combination of two ormore thereof. In a reaction between a cyclic hydroxyphosphazene compound(1b) and an epoxy compound, a terminal end of a copolymer produced fromthe reaction may be a hydroxy group or an epoxy group according to aquantitative relation therebetween.

[0081] Copolymer of Glycidylphophazene Compound (1c)) with ReactiveGroup Containing Compound

[0082] A copolymer between a glycidylphosphazene compound (1c) and areactive group containing compound can be produced by a reaction of aglycidylphosphazene compound (1c) with a reactive group containingcompound.

[0083] As epoxy compounds, there can be used epoxy compounds similar tothose used in a case of production of a copolymer between anaminophosphazene compound (1a) and/or a hydroxyphosphazene compound (1b)and an epoxy compound. Herein as well, epoxy compounds can be usedsingly or in a combination of two or more thereof. As concrete examplesof copolymers between a glycidylphosphazene compounds (1c) and an epoxycompound, there are named the following copolymers, for example, betweendiglycidyl ether of bisphenol A, or glycidyl ether of4,4′-(1,2-epoxyethyl)biphenyl, 2,2bis(3,4-epoxycyclohexyl)propane orresorcinol, or diglycidyl ether of phloroglucin or the like; andhexaglycidylphenoxy cyclotriphosphazene, hexaglycidylethylphenoxycyclotriphosphazene, a cyclotriphosphazene with a glycidyloxyphenoxygroup and a phenoxy group as substitutes in a mixed manner, acyclotriphosphazene with a glycidyloxyethylphenoxy group and a phenoxygroup as substitutes in a mixed manner, a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner, a linear phosphazene mixture (a mixtureof linear phosphazenes of the general formula (1) with n=3000 onaverage) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner or the like. In the copolymers, a terminalend of each polymer may be a phosphazene compound or an epoxy compound.These copolymers can be used singly or in a combination of two or morethereof.

[0084] As concrete examples of copolymers between a glycidylphosphazenecompound (1c) and a phenol compound, there are named the followingcopolymers, for example, between resins obtained by condensation ofbisphenol A, bisphenol F, dihydroxynaphthalene, phenol, cresol orxylenol and formaldehyde in the presence of an acidic catalyst, p-vinylphenol resin, triphenolmethane condensate or the like; andhexaglycidylphenoxy cyclotriphosphazene, hexaglycidylethylphenoxycyclotriphosphazene, a cyclotriphospazene with a glycidyloxyphenoxygroup and a phenoxy group as substitutes in a mixed manner, acyclotriphospazene with a glycidyloxyethylphenoxy group and a phenoxygroup as substitutes in a mixed manner, a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner, a linear phosphazene mixture (a mixtureof linear phosphazenes of the general formula (1) with n being 3000 onaverage) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner or the like. In the copolymers, a terminalend of each polymer may be a glycidyl group or a hydroxy group. Thecopolymers can be used singly or in a combination of two or morethereof.

[0085] As amine compounds, there may be named the following compoundssuch as diethylenetriamine, triethylenetetramine,tetraethylenepentamine, diethylaminopropylamine, polyamidepolyamine,menthenediamine, isophrone diamine, N-aminoethylpiperazine,bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane,m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,m-phenylenediamine, dicyandiamide, adipic acid dihydrazide, 3,9-bis(3-aminoporpyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct andothers. The amine compounds can be used singly or in a combination oftwo or more thereof.

[0086] As concrete examples of copolymers between a glycidylphosphazenecompound (1c) and an amine compound, there are named the followingcopolymers, for example, between an amine compound such astetraethylenepentamine, m-xylenediamine, diaminodiphenylmethane,diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide or the like;and hexaglycidylphenoxy cyclotriphosphazene, hexaglycidylethylphenoxycyclotriphosphazene, a cyclotriphospazene with a glycidylphenoxy groupand a phenoxy group as substitutes in a mixed manner, acyclotriphospazene with a glycidylethylphenoxy group and a phenoxy groupas substitutes in a mixed manner, a cyclophosphazene mixture (a mixtureof cyclophosphazenes of the general formula (1) with n being 3 to 15)with a glycidylphenoxy group and a phenoxy group as substitutes in amixed manner, a linear phosphazene mixture (a mixture of linearphosphazenes of the general formula (1) with n=3000 on average) with aglycidylphenoxy group and a phenoxy group as substitutes in a mixedmanner or the like. In the copolymers, a terminal end of each polymermay be a glycidyl group or an amino group. The copolymers can be usedsingly or in a combination of two or more thereof.

[0087] As acid anhydrides, there are named the following anhydrides, forexample, phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,methylhexahydrophthalic anhydride, methylnadic anhydride,dodecylsuccinic anhydride, chlorendic anhydride, pyromellitic anhydride,benzophenonetetracarboxylic anhydride, ethyleneglycolbis(anhydrotrimate), methylcyclohexanetetracarboxylic anhydride,trimellitic anhydride, polyazelaic anhydride and others. The anhydridescan be used singly or in a combination of two or more thereof. Asconcrete examples of copolymers between a glycidylphosphazene compound(1c) and an acid anhydride, there are named the following copolymers,for example, between tetrahydrophthalic anhydride, hexahydrophthalicanhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalicanhydride, pyromellitic anhydride, benzophenonetetracarboxylicanhydride, methylcyclohexanetetracarboxylic anhydride or the like; andhexaglycidylphenoxy cyclotriphosphazene, hexaglycidylethylphenoxycyclotriphosphazene, a cyclotriphosphazene with a glycidyloxyphenoxygroup and a phenoxy group as substitutes in a mixed manner, acyclotriphosphazene with a glycidyloxyethylphenoxy group and a phenoxygroup as substitutes in a mixed manner, a cyclophosphazene mixture (amixture of cyclophosphazenes of the general formula (1) with n being 3to 15) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner, a linear phosphazene mixture (a mixtureof linear phosphazenes of the general formula (1) with n=3000 onaverage) with a glycidyloxyphenoxy group and a phenoxy group assubstitutes in a mixed manner or the like. In the copolymers, a terminalend of each polymer may be a glycidyl group or an acid residue. Thecopolymers can be used singly or in a combination of two or morethereof.

[0088] (C) Component: Epoxy Hardener

[0089] As epoxy hardeners, there are named a compound having a phenolichydroxyl group, an aromatic amine compound, an acid anhydride andothers. Among them, preferable is a compound having a phenolic hydroxylgroup in consideration of moisture resistance, moldability, storagestability and others. As compounds each having a phenolic hydroxylgroup, there are named, without a specific limitation imposed oncompounds as far as the compounds show a curing action exerted to anepoxy resin, for example, resins obtained by condensation orco-condensation of a phenol such as phenol, cresol, xylenol, resorcinol,catechol, bisphenol A or bisphenol F, or a naphthol such as α-naphthol,β-naphthol or dihydroxynaphthalene with an aldehyde such asformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde orsalicylaldehyde in the presence of an acidic catalyst, p-vinyl phenolresin, phenol-aralkyl resin having a xylylene group, synthesized from aphenol and dimethoxy-p-xylene, dicyclopentadiene-modified phenol resin,triphenolmethane condensate and others. These can be used singly or in acombination of two or more thereof.

[0090] (D) Components: Inorganic Filler

[0091] An inorganic filler has a characteristic not only to enhance adripping preventive effect of a resin composition but to also improve amechanical strength thereof As inorganic filler, while any of inorganicfiller commonly used in this field can be employed, there can be namedthe following: for example, powder of fused silica, crystal silica,alumina, aluminum hydroxide, magnesium hydroxide, zinc oxide, zincborate, zircon, antimony trioxide, talc, calcium silicate, calciumcarbonate, silicon carbide, boron carbide, beryllia, zirconia, titaniumwhite, clay, mica, talc and others; beads produced from the abovepowder; kaolin, barium sulfate, barium carbonate, calcium sulfate,titanium oxide, glass beads, glass balloons, glass flakes, fibrousalkali metal titanate (sodium titanate fibers and others), fibrousborate (aluminum borate fibers, magnesium borate fibers and others),zinc oxide fibers, titanium oxide fibers, magnesium oxide fibers, gypsumfibers, aluminum silicate fibers, calcium silicate fibers, siliconcarbide fibers, titanium carbide fibers, titanium nitride fibers, carbonfibers, alumina-silica fibers, zirconia fibers, quartz fibers, thintitanate flakes, thin titanium dioxide flakes and others. The inorganicfiller can be used singly or in a combination of two or more thereof.

[0092] Compounding Proportions of Components

[0093] Compounding proportions of components (A) to (D) described abovein a composition of the present invention meet the following relation,in which, as to components of an epoxy resin (A), a phosphazene compound(B), an epoxy hardener (C) and an inorganic filler (D), the component(B) has only to be in the range of from 0.01 to 70% by weight andpreferably in the range of from 0.1 to 60% by weight and the component(B) has only to be in the range of from 0 to 70% by weight andpreferably in the range of from 0 to 60% by weight relative to a totalquantity of the components (A) to (C), and the component (D) has only tobe in the range of from 0 to 95% by weight and preferably in the rangeof from 0 to 90% by weight relative to a total quantity of thecomponents (A) to (D).

[0094] A type of epoxy resin and types of other components used togetherhave only to be selected within the ranges of compounding quantitiesdescribed above giving consideration to performance required of a targetflame-retardant epoxy resin composition, a type of a laminatemanufactured using the flame-retardant epoxy resin composition, types ofan encapsulating material and a material of a casting mold, and aneffect of further improving performance of flame retardance, moistureresistance, soldering heat resistance, mechanical properties andmoldability of a flame-retardant epoxy resin composition to be obtained.

[0095] While no specific limitation is placed on an equivalent ratio ofan epoxy resin (A) and a functional group of a component (C) (the numberof groups of (C)/the number of epoxy groups of (A)), the ratio ispreferably set in the range of from 0.7 to 1.3 in order to suppressrespective unreacted portions low.

[0096] Since a phosphazene compound as a (B) component works not only asa flame retardant but also as an epoxy resin or an epoxy hardener, anequivalent ratio of an epoxy resin as a component (A), a phosphazenecompound as a component (B) and a functional group of an epoxy hardeneras a component (C) are preferably all set in the range of from 0.7 to1.3.

[0097] Preferred embodiments of a flame-retardant epoxy resincomposition of the present invention will be shown below.

[0098] (1) A flame-retardant epoxy resin composition in which as tocomponents of an epoxy resin (A) and a phosphazene compound (B), thephosphazene compound component (B) is compounded in the range of from0.01 to 70% by weight (and preferably in the range of from 0.1 to 60% byweight) relative to a total quantity of the components (A) and (B).

[0099] (2) A flame-retardant epoxy resin composition in which as tocomponents of an epoxy resin (A), a phosphazene compound (B) and anepoxy hardener (C), the phosphazene compound component (B) is compoundedin the range of from 0.01 to 70% by weight (and preferably in the rangeof from 0.1 to 60% by weight) and the epoxy hardener component (C) iscompounded in the range of from 0 to 70% by weight (and preferably inthe range of from 0 to 60% by weight) relative to a total quantity ofthe components (A), (B) and (C).

[0100] (3) A flame-retardant epoxy resin composition in which as tocomponents of an epoxy resin (A), a phosphazene compound (B), an epoxyhardener (C) and an inorganic filler (D), the phosphazene compoundcomponent (B) is compounded in the range of from 0.01 to 70% by weight(and preferably in the range of from 0.1 to 60% by weight), the epoxyhardener component (C) is compounded in the range of from 0 to 70% byweight (and preferably in the range of from 0 to 60% by weight) relativeto a total quantity of the components (A), (B) and (C); and theinorganic filler component (D) is compounded in the range of from 0 to95% by weight (and preferably in the range of from 0 to 90% by weight)relative to a total quantity of the components (A), (B). (C) and (D).

[0101] (4) A flame-retardant epoxy resin composition in which a polymerof a cyclic and/or a chain phosphazene compound of the general formula(1) is compounded as a phosphazene compound (B) in any one of theflame-retardant epoxy resin compositions (1), (2) and (3)

[0102] (5) A flame-retardant epoxy resin composition obtained bycompounding any one of the flame-retardant epoxy resin compositions (1),(2), (3) and (4) into a thermoplastic resin and/or a thermoset resin.

[0103] Other Components

[0104] A curing accelerator may be included in a flame-retardant epoxyresin composition of the present invention in addition to the abovecomponents. As curing accelerators, there can be used accelerators knownin this field and there can be named the following, for example, basicactive hydrogen compounds such as dicyandiamide and adipic acidhydrazide; bicycloamidines such as 1,8-diazabicyclo(5,4,0)undecene-7 and1,5-diazabycyclo(3,4,0)nonene-5, and derivatives such as phenolatesthereof, octyl salts thereof and oleic acid salts thereof,oxyalkylamines such as triethanolamine, tetramethylbutanediamine,tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine,dimethylaniline, benzyl dimethylamine, dimethylaminoethanol anddimethylaminopentanol; tertiary amines such astris(dimethylaminomethyl)phenol, N-methylmorpholine andN-ethylmorpholine; imidazoles such as 2-methylimidazole,2-ethylimidazole, 2-phenylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 2-methyl-4-ethylimidazole,2-phenyl-4-methylimidazole, 1-butylimidazole, 1propyl-2-methylimidazole,1bezyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,1-azine-2-methylimidazole and 1-azine-2-uindecylimidazole; quaternaryammonium salts such as cetyl trimethyl ammonium bromide, cetyl trimethylammonium chloride, dodecyl trimethyl ammonium iodide, trimethyl decylammonium chloride, benzyl dimethyl tetradecyl ammonium chloride, benzylmethyl palmityl ammonium chloride, allyl dodecyl trimethyl ammoniumbromide and benzyl dimethyl tetradecyl ammonium acetate; organicphosphines such as tributyl phosphine, methyl diphenyl phosphine andtriphenyl phosphine; and tetraphenyl borates such as triphenylphosphinetetraphenyl borate, tetraphenylphosphonium tetraphenyl borate,triethylamine tetraphenyl borate, N-methylmorpholine tetraphenyl borate,2-ethyl-4-methylimidazole tetraphenyl borate and2-ethyl-1,4-dimethylimidazole tetraphenyl borate. The curingaccelerators can be used singly or in a combination of two or morethereof.

[0105] Fluororesin and others can be compounded into a flame-retardantepoxy resin composition of the present invention for the purpose toimprove flame-retardant performance, especially dripping (fire spreadingdue to dripping in burning) preventive performance to a higher level. Asfluororesin, there can be used known fluororesin which are named, forexample, polytetrafluoroethylene (PTFE),tetrafluoroethylene-hexafluoropropylene copolymer (FEP),tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA),tetrafluoroethylene-ethylene copolymer (ETFE),poly(trifluorochloroethylene) (CTFE), polyfluorovinylidene (PVdF) andothers. Among them, preferable is PTFE. Fluororesins can be used singlyor in a combination of two or more thereof. No specific limitation isplaced on a compounding quantity of fluororesin and in a case of acomposition of the present invention consisting of an epoxy resin (A), aphosphazene compound (B) and an epoxy hardener (C), a compoundingquantity of fluororesin is generally on the order in the range of from0.01 to 2.5% by weight and preferably on the order in the range of from0.1 to 1.2% by weight relative to a total quantity of the epoxy resin(A), the phosphazene compound (B) and the epoxy hardener (C), though acompounding quantity thereof can be properly selected in a wide rangeaccording to various conditions such as a type of an epoxy resin, aquantity of usage of a flame retardant, types and compounding quantitiesof other additive agents, an application for a flame-retardant resincomposition to be obtained.

[0106] Various types of additive agents can be compounded into aflame-retardant epoxy resin composition of the present invention in arange in which preferable characteristics thereof are not lost at anydegree. As the additive agents, there are named, for example, the curingaccelerator, natural waxes, synthetic waxes, straight-chain aliphaticacids and salts thereof, acid amides, esters, release agents such asparaffins, phosphazene compounds other than phosphazene compounds as thecomponents (B) of the present invention, phosphate esters, condensedphosphate esters, other organic phosphorus compounds; flame retardantssuch as phosphorus as an element, red phosphorus, chlorinated paraffin,brominated toluene, hexabromobenzene, antimony trioxide and otherinorganic flame retardants; colorants such as carbon black and red ironoxide; and coupling agents (silane coupling agents such as3-glycidoxypropyltrimethoxy silane and titanium based coupling agentssuch as tetraoctylbis(phosphite)titanate and others). The additives canbe used singly or in a combination of two or more thereof.

[0107] General resin additive agents can further be compounded into aflame-retardant epoxy resin composition of the present invention in arange in which preferable characteristics thereof are not lost at anydegree. While no specific limitation is imposed thereon, there arenamed, for example, ultraviolet absorbents such as benzophenone based,benzotriazole based, cyanoacrylate based, triazine based and others, alight stabilizing agent such as hindered amine based, anti-oxidants suchas hindered phenol, organic phosphorus based peroxide decomposing agent,organic sulfur based peroxide decomposing agent; light interceptingagents such as rutile type titanium oxide, zinc oxide, chromium oxide,cerium oxide and others; metal deactivating agents such as benzotriazolebased and others; quenching agents such as organic nickel compound andothers; an anti-cloudness agent, an anti-mold agent, an antibacterialagent, pigments and others.

[0108] A flame-retardant epoxy resin composition of the presentinvention can be produced by mixing and/or kneading prescribedquantities or proper quantities of an epoxy resin (A), a phosphazenecompound (B), an epoxy hardener (C), an inorganic filler (D) and, whenrequired, furthermore, fluororesin and other flame retardants accordingto a known method. Mixing of the components have only to be performed ina proper sequence of operations, and two or more types among mixedcomponent composites and single components may be mixed to one compoundprior to the usage.

[0109] As flame retardants for other synthetic resins, there may be usedone type or two or more types of polymers selected from the groupconsisting of the phosphazene compounds (1) and one type or two or moretypes selected from the group consisting of reaction products obtainedfrom a reaction of a phosphazene compound (1) with a reactive groupcontaining compound. As the synthetic resins, no specific limitation isplaced thereon but there can be used any one of known thermoplasticresin and/or thermoset resin. As concrete examples of thermoplasticresins, there are named the following resins: polyethylene,polypropylene, polyisoprene, chlorinated polyethylene, polyvinylchloride, polybutadiene, polystyrene, high-impact polystyrene,acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styreneresin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBSresin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABSresin), acrylonitrile-acrylic rubber-styrene resin (AAS resin),poly(methyl (meta)acrylate), polyester (polyethylene terephthalate,polybutylene terephthalate, polyethylene naphthalate and others),polycarbonate, polyphenylene ether (PPE), modified polyphenylene ether,polyamide (aliphatic and/or aromatic), polyphenylene sulfide, polyimide,poly(ether ether ketone), polysulfone, polyallylate, poly(ether ketone)poly(ether nitrile), poly(thioether sulfone), poly(ether sulfone),polybenzimidazole, polycarbodiimide, polyamidimide, poly(etherimide), aliquid crystal polymer and others. Among them, preferable are polyester,ABS resin, polycarbonate, modified polyphenylene ether, polyamide andothers. As concrete examples of thermoset resins, there are named thefollowing resins: for example, polyurethane, phenol resin, melamineresin, bismaleimide-triazine resin, urea resin, unsaturated polyesterresin, diallyl phthalate resin, silicone resin, epoxy resin (bisphenol-Aepoxy resin, bisphenol-F epoxy resin, bisphenol-AD epoxy resin, phenolnovolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic epoxyresin, glycidyl ester based epoxy resin, glycidyl amine based epoxyresin, heterocyclic epoxy resin, urethane-modified epoxy resin,brominated bisphenol-A epoxy resin and others) and others. Among them,preferable are polyurethane, phenol resin, melamine resin, epoxy resinand others and especially preferable is epoxy resin. The thermoplasticresins and the thermoset resins each are employed singly or in acombination of two or more thereof. No specific limitation is placed ona compounding quantity of a flame retardant into a synthetic resin, butthe flame retardant quantity thereof is generally on the order in therange of from 0.01 to 100 parts by weight and preferably on the order inthe range of from 0.5 to 60 parts by weight relative to 100 parts byweight of a synthetic resin, though a compounding quantity thereof canbe properly selected in a wide range according to various conditionssuch as types of a synthetic resin and a flame retardant, a type and acompounding quantity of another additive agent, required performance, anapplication and others of a resin composition to be obtained. In theresin composition, there can be compounded one type or two or more typesof additive agents selected from the group consisting of the componentsshown in the section of [Inorganic filler] and the various additivesshown in the section of [Other components]. The resin composition can beproduced by mixing and/or kneading a synthetic resin, a flame retardantand when required, other additive agents. Furthermore, molded articlesof various shapes can be formed using common molding means for syntheticresin.

[0110] Moreover, a flame-retardant epoxy resin composition of thepresent invention may be compounded into one of the various types ofsynthetic resin described above to produce a new flame-retardant resincomposition.

[0111] In a case where a flame-retardant epoxy resin composition of thepresent invention is compounded into a thermoplastic and/or a thermosetresin, a mixture composed of various types of components in the form ofpowder, beads, flakes or pellets has only to be mixed and/kneaded into acompound using an extruder such as a single screw extruder, a doublescrew extruder or the like, a Banbury mixer, a pressure kneader, or akneader with a twin-roll type or the like. Then, a molded article of anyshape can be produced according to a known molding method such as pressmolding, injection molding, extrusion molding, casting or the like.

[0112] Applications

[0113] An flame-retardant epoxy resin composition of the presentinvention thus obtained can be applied to various types of fields wherea synthetic resin can be used and used especially as electronic partmaterials such as laminate material, encapsulating material, opticalmaterial, casting material and others in fields of electrical,electronic and communication equipment, and precision equipment.Furthermore, a flame-retardant epoxy resin composition of the presentinvention can be applied in common ways of usage of an epoxy resin suchas paint, adhesive agent, a transportation vehicle and equipment, fiberproducts, various types of fabrication machines, food packaging filmsand a vessel, articles associated with agriculture, forest and fishery,materials for civil engineering and building, medical supplies,components of furniture; composite material for aerospace use andothers.

[0114] More detailed description will be given for applications aselectronic parts in fields of electrical, electronic and communicationequipment, and precision equipment.

[0115] (1) Prepreg and Copper Clad Laminate

[0116] A flame-retardant epoxy resin composition of the presentinvention is used in paper base copper clad laminate, a glass cloth basecopper clad laminate, composite copper clad laminate, a flexible copperclad laminate and others to construct an electronic part. A laminate canbe fabricated using a known method. For example, a process goes thisway: a proper sheet-like substrate such as glass cloth is impregnatedwith a varnish including a flame-retardant epoxy resin composition ofthe present invention to form a prepreg and thereafter, prepregs areused to fabricate a copper clad laminate or the like.

[0117] As sheet like substrates for use in preparation of prepreg,substrates that are commonly used in this field can be used, which arenamed, for example,: glass woven cloth, glass non-woven cloth and clothcomposed of components other than a glass such as paper or aramidfibers.

[0118] A varnish used for fabricating a prepreg can be prepared bydissolving an epoxy resin composition of the present invention into anorganic solvent. As organic solvents, no specific limitation is imposedthereon as far as an epoxy resin composition of the present inventioncan be dissolved thereinto, which are named, for example, toluene,xylene, acetone, methylethyl ketone, methylisobutyl ketone,N,N,-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide,trichloroethylene, trichloroethane, methylene chloride, dioxane, ethylacetate and others. Furthermore, various types of coupling agents may beadded into a varnish in order to improve a close adherence ability on asheet-like substrate.

[0119] One to several prepregs obtained are placed between two copperfoils and the prepregs with the two copper foils are hot pressed at atemperature of the order between 100 to 250° C. under pressure between0.1 to 10 MPa to mold, thereby fabricating a double sided copper cladsubstrate for conductive circuit formation. After a circuit pattern isformed on the double sided substrate, a necessary number of double sidedcopper clad substrates are placed between the prepreg sheets, and thesubstrates and the sheets are hot pressed at a temperature of the orderbetween 100 to 250° C. under a pressure between 0.1 to 10 MPa foradhesion-molding to obtain a multilayer board. After theadhesion-molding, holes for interlayer conduction are formed in themultilayer board, the holes are copper plated to achieve interlayerconduction and a conductor of the outermost layer is formed, therebyenabling a copper laminate to be obtained.

[0120] (2) Build-Up Type Multilayer Printed Wiring Board

[0121] A flame-retardant epoxy resin composition of the presentinvention is used as materials of a build-up type multilayer printedwiring board, for example, materials of an interlayer insulating film, asolder resist, a resin coated copper foil and others to construct anelectronic part.

[0122] To be concrete, a flame-retardant epoxy resin composition of thepresent invention and other components when required are at firstdissolved into a proper organic solvent such as toluene, methylethylketone, methylcellosolve or the like to prepare a varnish, the varnishis applied on a copper foil or a carrier film such as made of polyesteror polyimide to dry the varnish coat by heating and to therebysemi-harden the coat, which is a common method, thus fabricating acarrier-provided resin film. Then, carrier-provided resin films are,according to a common method, laminated on an inner layer circuit sheet(a glass epoxy laminate) serving as a core by heating under pressurewith a laminator, one of various types, to obtain a build-up typemultilayer printed wiring board.

[0123] In a case where a component to be cured by energy rays such asultraviolet rays or electron rays is contained in a flame-retardantepoxy resin composition of the present invention, the composition can beused as solder resist material (solder resist ink) capable of developingand printing.

[0124] (3) Adhesive Agent and Flexible Printed Wiring Board

[0125] By applying a flame-retardant epoxy resin composition of thepresent invention on a heat resistant resin film or a conductive foil asan adhesive agent for a electronic part, there can be obtained aflexible printed wiring board such as a single sided flexible printedwiring board, a double sided flexible printed wiring board, a multilayerflexible printed wiring board and others. As heat resistant resin films,while no specific limitation is placed thereon as far as the films areself-extinguishing and contain no halogen, there are named polyimidefilm, polyethyleneterephthalate film, polyethylenenaphthalate film andothers among which a polyimide film is especially preferable from theviewpoint of heat resistance, mechanical properties, electricalcharacteristics, a flame retardance and others. As conductive foils,there are named a copper foil, an aluminum foil, a nickel foil, astainless foil, alloy foils such as an iron-nickel foil and others,among which a copper foil is especially preferable in an aspect offlexibility, electrical characteristics, machinability and others.

[0126] (4) Anisotropic Conductivity Material

[0127] A flame-retardant epoxy resin composition of the presentinvention is used in an adhesive agent with anisotropic conductivity, asheet with anisotropic conductivity, a film with anisotropicconductivity, a paste material with anisotropic conductivity and thelike for use in electrical connection of a finely patterned circuit of aliquid crystal display (LCD) and a tape carrier package (TCP), TCP and aprinted circuit substrate (PCB) and others, thus constructing anelectronic part.

[0128] (5) Semiconductor Encapsulating Material and Opto-DeviceEncapsulating Material

[0129] A flame-retardant epoxy resin composition of the presentinvention is used in a semiconductor encapsulating material and anopto-device encapsulating material, for example film semiconductorencapsulating material, high thermal conductivity semiconductorencapsulating material, area bump package encapsulating material, bumpbonding structure encapsulating material, flip chip encapsulatingmaterial, lead-free solder encapsulating material, flip chip mountingunder-fill material, wafer-level under-fill material, photo-couplerencapsulating material and others to construct an electronic part. Asproducts obtained by using a flame-retardant epoxy resin composition ofthe present invention, there can be exemplified: IC, LSI, VLSI,thyrister, diode, TSOP (Thin Small Outline Package), BGA (Ball GridArray), CSP (Chip Scale/Size Package), COF(Chip On Film/FPC) and others.

[0130] As opto-device material, a flame-retardant epoxy resincomposition of the present invention can be used as encapsulatingmaterial for fabrication of LED, a photodiode, a phototransistor, CCDand others.

[0131] (6) Optical Material and Casting Material

[0132] A flame-retardant epoxy resin composition of the presentinvention is used in an optical material of an interlayer insulatingfilm for an element of a liquid crystal display of a segment type, asimple matrix scheme or an active matrix scheme and in encapsulatingmaterial for an element of a liquid crystal display, thus constructingan electronic part. Furthermore, a flame-retardant epoxy resincomposition of the present invention can be used as a casting materialin a coil insulating material for a relay, a motor, a transformer, anantenna and others.

[0133] Electronic parts described above are subjected to any suitableelectrical treatment and machining to follow and further used in thefollowing applications, which are, for example, a printer, a computer, aword processor, a key board, a compact information terminal equipment(PDA), a telephone, a portable telephone, a facsimile, a copier, anelectronic cash register (ECR), a hand held calculator, an electronicnotepad, an electronic dictionary, a card, a holder, an administrativeand OA equipment including stationary, a washer, a refrigerator, acleaner, a microwave oven, a lighting fixture, a game machine, an iron,home electrical appliance such as electric foot warmer, a televisionset, VTR, a video camera, a radio cassette player, a tape recorder, amini-disk player, a CD player, a DVD player, a speaker, AV equipmentsuch as a liquid crystal display, an EL display, a plasma display andothers, a connector, a relay, a capacitor, a switch, a coil bobbin, abattery, a CCD sensor, an electric wire, a cable, electrical andelectronic parts such as a transformer, a motor, an antenna coil, adeflection york, a distribution board, a clock-and others, andcommunication equipment such as non-contact data carrier package system,and others.

[0134] In addition, as other applications of compositions of the presentinvention, the compositions are processed into molded articles andincorporated into various types of construction materials such as anadhesive agent and a paint, and there are exemplified the followingitems, which are: materials for an automobile, a vehicle, a ship, an airplane and building such as various types of packing in and a top clothof a chair or a seat; a belt, ceiling and wall boards, a convertibletop, an arm rest, a door trim board, a rear package tray, a carpet, amat, a sun visor, a wheel cover, a mattress cover, an air bag, aninsulating material, a hand grasp, a hand strap, wire covering material,electrically insulating material, paint, coating material, facingmaterial, flooring, a corner wall, a carpet, wall paper, wall facingmaterial, outer facing material, inner facing material, roofing, a soundinsulating board, heat insulating board, window shade or curtain; andequipment and supplies for daily life and sports such as clothes,curtain, bed sheets, plywood, a synthetic fiber plate, carpet, a mainentrance mat, a sheet, a bucket, a hose, a container, eyeglasses, a bag,a case, goggles, a ski, a snowboard, a skateboard, a racket, a tent anda musical instrument.

EXAMPLES

[0135] Then, there will be shown synthetic examples, examples andcomparative examples and therewith, detailed description will be givenof the present invention. Evaluation of various aspects of performancewas valued as measured according to the following schemes.

[0136] 1. Thermal Deformation Temperature

[0137] The temperature was measured in conformity with ASTM D-648 with aload of 1.82 Mpa, which is used as an index for heat resistance.

[0138] 2. Flame Retardance

[0139] A test piece of a size of {fraction (1/16)} inch in thickness, 5inch in length and 0.5 inch in width was prepared and an evaluation testfor flame retardance was applied to the test piece according to UL-94standard (Test for Flammability of Plastic Materials for Parts inDevices and Appliances UL94, Fourth Edition). Definitions of terms andevaluation criteria used in UL94 are as follows:

[0140] Definitions of Terms

[0141] Afterflame is that flaming (burning with a flame) of a materialafter contact of a flame (after removing an igniter) is sustained.

[0142] An afterflame time is a length of a time during which a materialis burning with a flame after contact of a flame under test conditions.

[0143] Afterglow is that after flaming is over or after contact of aflame unless flaming occurs, glowing of a material (though not burnedwith a flame, being kept in a red heat state serving as an igniter) issustained as is.

[0144] An afterglow time is a length of a time during which aftercontact of a flame and/or after flaming is over, a material is kept in aread heat state serving as an igniter under test conditions.

[0145] t1 is an afterflame time after a first flaming operation,

[0146] t2 is an afterflame time after a second flaming operation and

[0147] t3 is an afterglow time after the second flaming operation.

[0148] Evaluation Criteria

[0149] 94 V-0

[0150] (1) afterflame times t1 or t2 of each of test pieces is 10 sec orless,

[0151] (2) the sum (t1+t2) of afterflame times of 5 test pieces is 50sec or less,

[0152] (3) the sum (t2+t3) of an afterflame time and an afterglow timeof each of test pieces after the second flaming operation is 30 see orless,

[0153] (4) afterflame or afterglow of any test piece does not reach afixation clamp, and

[0154] (5) a sign of cotton is not ignited by a flaming particle ordroppings.

[0155] As thermoplastic resin, thermoset resin and fluororesin, thefollowing resins were employed:

[0156] Epoxy resin: phenol novolak epoxy resin made by DAINIPPON INKKABUSHIKI KAISHA with a trade name of Epiclon N-770,

[0157] Epoxy resin: cresol novolak epoxy resin with an epoxy equivalentof 215 g/eq.,

[0158] Phenol resin: a hydroxyl equivalent of 106 g/eq.,

[0159] Aromatic polycarbonate resin made by Mitsubishi EngineeringPlastics Corp with a trade name of Jupilon S-2000N

[0160] ABS resin made by Mitsui Chemical Corp. with a trade name ofSantac UT-61, and

[0161] Polytetrafluoroethylene (PTFE) made by Asahi Glass Co., Ltd. witha trade name of G-307.

Synthetic Example 1 (Synthesis of a Raw Material Phosphazene)

[0162] Into a 10L flask equipped with a reflux condenser, a thermometer,a stirrer, a phosphorous trichloride dropper and a chlorine gas blowingpipe, 5 L of chlorobenzene, 365 g (6.8 mol) of ammonium chloride and 5.0g of zinc chloride were put to obtain a mixed dispersion liquid. Thedispersion liquid was heated to a temperature of 130° C. and 851 g ofphosphorous trichloride was dropped thereinto at the temperate underreflux at a feed rate of 8.9 g/min over 96 min and 454 g of chlorine gaswas simultaneously fed thereinto at a feed rate of 4.7 g/min over 96min. After phosphorus trichloride and chlorine gas were fed, thedispersion liquid was refluxed at temperature of 132° C. for another 144min to complete a reaction. Then, the dispersion liquid was subjected tosuction filtration to remove non-reacted ammonium chloride and afiltrate was distilled under a reduced pressure of 1.3 to 2.7 hPa at 30to 40° C. to remove chlorobenzene as a distillate and to obtain 704 g ofa reaction product. A yield of the reaction product was 98.1% relativeto the dropped phosphorous trichloride. The reaction product wasdissolved into chlorobenzene and recryatallization was performed toobtain 452 g of a mixture of 76% hexachlorocyclotriphosphazene and 24%octachldrocyclotetraphosphazene. A residual chlorobenzene solution leftafter recrystallization is concentrated to obtain 249 g of cyclic andchain chlorophosphozenes (a mixture in the general formula (1) with nbeing 3 to 15, where R¹O-group and R²O-group are substituted withchlorine atoms). Furthermore, the mixture ofhexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene wererecrystallized three times with hexane to obtain 312 g ofhexachlorocyclotriphosphazene of a purity 99.9%.

Synthesis Example 2 (Synthesis of Phosphazene (A) Having Amino Groups atsome but not all Sites)

[0163] Into a 2 L four-necked flask equipped with a reflux condenser, athermometer, a stirrer and a dropping funnel, 208.7 g (1.5 mol) of4-nitrophenol, 141.2 g (1.5 mol) of phenol, 303.6 g (3.0 mol) oftriethylamine and 1200 mL of tetrahydrofuran (THF) were put to obtain asolution. Then, a solution of 116 g (1 unit mol, NPCl₂ is 1 unit) ofhexachlorocyclotriphosphazene of a purity 99.9% in 300 mL of THF wasdropped into the THF solution of 4-nitrophenol, phenol and triethylamineover 2 hours while cooling the solution properly by stirring so that areaction temperature is 30° C. or lower. After the dropping, thereaction was successively continued at room temperature for another 12hours while stirring the solution. Then, the reaction was furtherperformed at a reflux temperature of the solvent for another 6 hours tocomplete the reaction. After the reaction ended, a solid(cyclotriphosphazene with a nitrophenoxy group and a phenoxy group assubstitutes in a mixed manner and triethylamine hydrochloric acid salt)was filtered out and the solid was repeatedly washed with 2% potassiumhydroxide aqueous solution at 40° C. and water sufficient times tillwater used in the last washing became neutral. After vacuum drying,there was obtained 272.0 g of a yellow solid at a yield of 98%. Aresidual chlorine quantity is 0.01% or less and synthesis of thecompound was confirmed by performing ¹H- and ³¹P-NMR analysis. Astructure thereof was [NP(OC₆H₄)_(0.97)(OC₆H₄NO₂)_(1.03)]₃ as the resultof the

[0164] Into a 1 L four-necked flask, 83.3 g (0.3 unit mol) of acyclotriphosphazene with a nitrophenoxy group and a phenoxy group assubstitutes in a mixed manner obtained according to the above process,5.0 g of active charcoal, 0.5 g of ferric chloride 6 hydrate salt and600 mL of THF were put and the solution was heated as a pretreatmentunder reflux for 10 min. Then, 37.6 g (0.6 mol) of 80% hydrazine hydratewas added to the solution, followed by a reaction at a refluxtemperature for 8 hours. After the reaction ended, the charcoal wasfiltered out and a filtrate was concentrated and dried to obtain 71.8 gof a light yellow solid at a yield of 97%. A change from a nitro groupto an amino group was confirmed by performing ¹H- and ³¹P-NMR analysis.A structure thereof was [NP(OC₆H₄)_(0.97)(OC₆H₄NH₂)_(1.03)]₃ as theresult of the analysis. An amino value (active hydrogen equivalent) ofthe compound was measured according to a common method and a result was120 g/eq.

Synthesis Example 3 (Synthesis of Phosphazene (B) Having Amino Groups atsome but not all Sites)

[0165] A phosphazene having amino groups at some but not all sites in ayellow solid state was obtained to a weight of 75.2 g (at a total yieldof 94%) in a similar process to Synthesis Example 2 except for use of87.6 g (0.3 unit mol) of cyclic and chain clorophosphazenes produced inSynthesis Example 1 (a mixture in the general formula (1) with n being 3to 15, where R¹O-group and R²O-group are substituted with chlorineatoms) instead of hexachlorocyclotriphosphazene and 299.7 g (1.5 mol) of4-nitromethylphenol instead of 4-nitophenol. A structure thereof was[NP(OC₆H₄)_(0.97)(OC₆H₄CH₂ NH₂)_(1.03)]₃ as the result of ¹H- and³¹P-NMR analysis. An amino value (active hydrogen equivalent)of thecompound was measured according to a common method and a result was 127g/eq.

Synthetic Example 4 (Synthesis of Phosphazene (C) Having Hydroxy Groupsat some but not all Sites)

[0166] Into a 2 L four-necked flask equipped with a reflux condenser, athermometer, a stirrer and a dropping funnel, 116 g (1 unit mol, NPCl₂is 1 unit) of a mixture of 82% hexaclorocyclotriphosphazen and 18%octaclorocyclotetraphosphazen and 200 mL of THF were put to obtain asolution. Then, a THF solution of 4-methoxyphenol sodium salt preparedseparately (126.5 g (1.1 mol) of 4-methoxyphenol, 23 g (1 g-atom) ofsodium and 400 mL of tetrahydrofuran) was dropped while stirring intothe TFT solution of the mixture of hexachlorocyclotriphosphazene andoctaclorocyclotetraphosphazen over 1 hour. Since there were observed aviolent heat release, the reaction was performed while properly coolingthe solution so that a reaction temperature does not exceed 30° C. Afterthe dropping, the reaction was successively continued at 60° C. foranother 6 hours while stirring the solution. A residual chlorinequantity of a partially substituted compound obtained by the reactionwas at 17.17% and an estimated structure thereof was[NPCl_(0.99)(OC₆H₄OCH₃)_(1.01)]_(3,4).

[0167] Then, a THF solution of sodium salt of p-cresol preparedseparately (140.6 g (1.3 mol) of p-cresol, 28.8 g (1.2 mol) of sodiumand 400 ml of THF) was dropped into the solution of the partiallysubstituted compound over 1 hour while controlling a reactiontemperature so as to be at 30° C. or lower by cooling. Then, thereaction was performed for 5 hours at room temperature and furthermorefor another 3 hours at a reflux temperature to complete the reaction.After completion of the reaction, THF as a solvent was removed under areduced pressure as a distillate, 1 L of toluene was added to theproduct to again dissolve and furthermore, 500 mL of water was added towash the product, followed by liquid separation. An organic layer waswashed with a 5% sodium hydroxide aqueous solution once and further witha 2% sodium hydroxide aqueous solution once, and thereafter, washed witha (1+9) hydrochloric acid aqueous solution once, washed with 5% sodiumhydrogencarbonate aqueous solution once, and washed with water twice tocause a pH value of a water layer to be neutral. Then the organic layerwas separated and dehydrated with anhydrous magnesium sulfate, followedby removal of toluene as distillate to obtain 270.8 g (at a yield of98%) of a product in a light yellow oily state. A residual chlorinequantity is 0.01% or lower.

[0168] Into a 2 L four-necked flask, 247.9 g (0.9 unit mol) of acyclophosphazene with a 4-methoxyphenoxy group and 4-methylphenoxy groupas substitutes in a mixed manner obtained according to the above processand 1040.0 g (9.0 mol) of pyridine hydrochloric acid salt were put and atemperature of the mixture is gradually raised, followed by a reactionat a temperature in the range of 205 to 210° C. for 1 hour. Aftercooling the mixture down to room temperature, 300 mL of water was addedthereto to dissolve a reaction product and excessive pyridinehydrochloric acid salt and further a pH value of the mixture wasadjusted to 6 to 7 with a 20% sodium hydroxide aqueous solution toprepare a reaction solution. Then, extraction was performed on thereaction solution with 1 L of ethyl acetate 4 times, thereafter thecollected extracts were combined and washed with 1 L of water saturatedwith sodium sulfate four times, an organic layer was separated and theorganic layer was dehydrated with anhydrous magnesium sulfate, followedby removal of ethyl acetate under a reduced pressure as distillate.Then, the concentrate was dissolved into 300 ml of methanol and thesolution was added into 3 L of water to thereby precipitate a crystal,which process was repeated three times, followed by vacuum drying of thecrystal obtained by the precipitation to obtain 200.0 g (a yield of 85%)of a light yellow crystal. A residual chlorine quantity in the productis at 0.01% or lower and a quantity of hydroxyl group (OH in %) wasquantified according to acetylation method using acetic anhydride andpyridine described on page 316 in Analytical Chemistry Handbook, organicversion (compiled by Society of Japan Analytical Chemistry) to obtain avalue of 6.5% (the theoretical value of 6.6%). Synthesis of the compoundwas confirmed by performing ¹H- and ³¹P-NMR analysis. An estimatedstructure thereof was [NP(OC₆H₄CH₃)_(0.99)(OC₆H₄OH)_(1.01)]_(3,4). Ahydroxyl group value of the compound was 259 g/eq.

Synthetic Example 5 (Synthesis of Phosphazene (D) Having HydroxyethylGroups at some but not all Sites)

[0169] Into a 2 L four-necked flask equipped with a reflux condenser, athermometer, a stirrer and a dropping funnel, 116 g (1 unit mol, NPCl₂is 1 unit) of a mixture of 82% hexachlorocyclotriphosphazene and 18%octaclorocyclotetraphosphazen and 200 mL of THF were put to obtain asolution. Then, a THF solution of phenol sodium salt prepared separately(103.5 g (1.1 mol) of phenol, 23 g (1 g-atom) of sodium and 400 mL oftetrahydrofuran) was added dropwise while cooling by stirring into theTHF solution of the mixture of hexachlorocyclotriphosphazene andoctaclorocyclotetraphosphazen over 1 hour. After the dropping, thereaction was successively performed at 60° C. for another 6 hours whilestirring the solution. A residual chlorine quantity of a partiallysubstituted compound obtained by the reaction was at 20.16% and anestimated structure thereof was [NPCl_(0.99)(OC₆H₄)_(1.01)]_(3,4).

[0170] A THF solution of 4-hydroxyethylphenolate prepared separately(179.6 g (1.3 mol) of 4-hydroxyethylphenol, 28.8 g (1.2 mol) of sodiumand 400 ml of THF) was added dropwise into the solution of the partiallysubstituted compound over 1 hour while controlling a reactiontemperature so as to be at 30° C. or lower by cooling. Then, thereaction was performed for 5 hours at room temperature and furthermorefor another 6 hours at a reflux temperature to complete the reaction.After completion of the reaction, THF as a solvent was distilled offunder a reduced pressure, then 1 L of toluene was added to the productto redissolve the product and furthermore 500 mL of water was added towash the product, followed by liquid separation. An organic layer waswashed with a 5% sodium hydroxide aqueous solution once and furthermorewith a 2% sodium hydroxide aqueous solution once, and thereafter, washedwith a (1+9) hydrochloric acid aqueous solution once, washed with 5%sodium hydrogencarbonate aqueous solution once, and washed with watertwice to cause a pH value of the water layer to be neutral. Then theorganic layer was separated and dehydrated with anhydrous magnesiumsulfate, followed by distillation of toluene to obtain 250.2 g (at ayield of 91%) of a product in a light yellow oily state. A residualchlorine quantity of the product is 0.01% or lower and synthesis of thecompound was confirmed by performing ¹H- and ³¹P-NMR analysis. Ahydroxyl group content was 6.0% (a theoretical value of 6.1%). Anestimated structure thereof was[NP(OC₆H₄CH₂CH₂OH)_(0.99)(OC₆H₄)_(1.01)]_(3,4). A hydroxyl group valueof the compound was 278 g/eq.

Synthetic Example 6 (Synthesis of Phosphazene (E) Having Glycidyl Groupsat some but not all Sites)

[0171] Into a 1 L reactor equipped with a stirrer, a reflux condenserand a thermometer, 78.4 g (0.3 unit mol) of phosphazene (C) havinghydroxy groups at some but not all sites obtained in Synthesis Example 4and 277.6 (3 mol) of epichlorohydrin were put to heat and dissolve.Then, a 40% sodium hydroxide aqueous solution (12 g (0.30 mole) ofsodium hydroxide) was added dropwise to the phosphazene solution at atemperature in the range of 95 to 118° C. over 60 min. The reaction wasperformed at the same temperature for another 15 min to complete thereaction. After completion of the reaction, epichlorohydrin and waterwere distilled off, 1 L of chloroform and 1 L of water were added to thereaction solution, followed by washing with water twice. An organiclayer separated was dehydrated with anhydrous magnesium sulfate,followed by distillation of chloroform to obtain 87.7 g of a lightyellow solid at a yield of 92%. Synthesis of the compound was confirmedby performing ¹H- and ³P-NMR analysis. An estimated structure thereofwas [NP(OC₆H₄CH₃)_(0.99)(OC₆H₄OGly)_(1.01)]_(3,4) (where Gly indicates aglycidyl group and this applies hereinafter in the description). Anepoxy equivalent of the compound was 315 g/eq.

Synthetic Example 7 (Synthesis of Phosphazene (F) Having Glycidyl Groupsat some but not all Sites)

[0172] A phosphazene having glycidyl groups at some but not all sites ina yellow solid state was obtained to a weight of 92.2 g (at a yield of93%) in a similar process to Synthesis Example 6 except for use of 82.5g (0.3 unit mol) of a phosphazene (D) having hydroxyethyl groups at somebut not all sites obtained in Synthesis Example 5. Synthesis of thecompound was confirmed by performing ¹H- and ³¹P-NMR analysis. Anestimated structure thereof was[NP(OC₆H₄CH₂CH₂OGly)_(0.99)(OC₆H₄)_(1.01)]_(3,4). An epoxy equivalent ofthe compound was 333 g/eq.

Synthetic Example 8 (Synthesis of Phenoxyphosphazene Compound (K))

[0173] Into a 1L four-necked flask equipped with a stirrer, athermometer and a reflux condenser, 123.0 g (1.3 mol) of phenol wasadded and further 500 ml of THF was added to form a homogeneoussolution. Then, 27.6 g of metallic sodium was put into the solution at atemperature of 25° C. or lower and thereafter, a temperature of thesolution was raised to 61° C. over 1 hour after input of metallicsodium, followed by stirring the solution at a temperature from 61 to68° C. for 6 hours, thereby preparing a sodium phenolate solution.

[0174] In parallel to the above reaction, 58.0 g (0.5 unit mol) of amixture of hexachlorocyclotriphosphazene andoctachlorocyclotetraphosphazene (76% a trimer and 24% a tetramer) weredissolved into 250 mL of THF in a 2 L four-necked flask and the sodiumphenolate solution prepared as described above was added dropwise intothe solution of the mixture in a state being stirred at a temperature of25° C. or lower. After the dropping ended, a reaction was caused in themixture solution at a temperature from 71 to 73° C. for 15 hours whilestirring. After completion of the reaction, the reaction mixture wasconcentrated and further redissolved into 500 ml of toluene, thereafterwashed with water, washed with a 5% sodium hydroxide aqueous solutionthree times, washed with a 5% hydrochloric acid aqueous solution, washedwith a 5% sodium hydrogencarbonate aqueous solution and washed withwater three times, followed by concentration and drying of the reactionmixture to obtain 109 g (at a yield of 94%) of a light yellow solid.

[0175] A residual chorine quantity (Hy-Cl) was 0.07% and it wasconfirmed that the product (K) was the following compound by performing¹H- and ³¹P-NMR analysis:

[N=P(—OPh)₂]_(3,4).

[0176] Synthetic Example 9 (Synthesis of Phosphazene Polymer (G))

[0177] Into a 1L reactor equipped with a stirrer, a reflux condenser anda thermometer, 78.3 g (0.3 unit mol) of a phosphazene (A) having aminogroups at some but not all sites: [NP(OC₆H₄)_(0.97)(OC₆H₄NH₂)_(1.03)]₃obtained in Synthesis Example 2, 105.5 g (0.31 mol) of bisphenol-Adiglycidyl ether, 1.0 g of triethanolamine and 700 mL of THF were putand a reaction was performed in the solution under reflux for 6 hours.After completion of the reaction, the reaction solution was concentratedand dried to obtain 180.1 g of a yellow solid. An IR analysis wasperformed to confirm the absence of a glycidyl group in the product.

Synthetic Example 10 (Synthesis of Phosphazene Polymer (H))

[0178] A phosphazene polymer (H) in a yellow solid state was obtained toa weight of 184.2 g in a similar process to Synthesis Example 9 exceptfor use of 82.5 g (0.3 unit mol) of a mixture (D) of acyclotriphosphazene and a cyclotetraphosphazene having a hydroxyethylgroup, [NP(OC₆H₄CH₂CH₂OH)_(0.99)(OC₆H₄)_(1.01)]_(3,4), obtained inSynthesis Example 5. An IR analysis was performed to confirm the absenceof a glycidyl group in the product.

Synthetic Example 11 (Synthesis of Phosphazene Polymer (I))

[0179] Into a 1L reactor equipped with a stirrer, a reflux condenser anda thermometer, 190.7 g (0.6 unit mol) of a mixture (E) of acyclotriphosphazene and a cyclotetraphosphazene each having a glycidylgroup, [NP(OC₆H₄CH₃)_(0.99)(OC₆H₄OGly)_(1.01)]_(3,4), obtained inSynthesis Example 6, 1.0 g of triethanolamine and 700 mL of THF were putand a reaction was caused in the solution under reflux for 6 hours.After completion of the reaction, the reaction solution was concentratedand dried to obtain 181.9 g of a yellow solid. An IR analysis wasperformed to confirm the absence of a glycidyl group in the product.

Synthetic Example 12 (Synthesis of Phosphazene Polymer (J))

[0180] Into a 1L reactor equipped with a stirrer, a reflux condenser anda thermometer, 99.1 g (0.3 unit mol) of a mixture (F) of acyclotriphosphazene and a cyclotetraphosphazene each having a glycidylgroup, [NP(OC₆H₄CH₂CH₂OGly)_(0.99)(OC₆H₄)_(1.01)]_(3,4), obtained inSynthesis Example 7, 28.2 g (0.3 mol) of phenol, 1.0 g oftriethanolamine and 700 mL of THF were put and a reaction was performedin the solution under reflux for 6 hours. After completion of thereaction ended, the-reaction solution was concentrated and dried toobtain 123.5 g of a yellow solid. An IR analysis was performed toconfirm the absence of a glycidyl group in the product.

Example 1

[0181] N.N′-dimethylformamide was added to 100 parts by weight of phenolnovolak epoxy resin, 63 parts by weight of a phosphazene compound (A)prepared in Synthesis Example 2 and 0.2 part by weight oftriphenylphosphine to prepare a varnish having a non-volatile matterconcentration of 60%. Using the varnish, 100 parts of glass cloth of0.18 mm in thickness made by NITTO BOSEKI CO. LTD. was impregnated with85 parts of the varnish as solid matter, and the impregnated glass clothwas dried for 5 min in a drying furnace at 150° C. to fabricate aprepreg of a resin content of 45.9%. Six pieces of prepreg thusfabricated were superimposed on one another, two electrolytic copperfoils of 35 μm in thickness were further superimposed on the top andbottom sides thereof, the superimposed intermediate was subjected to hotpressure molding at 190° C. under a pressure of 4 Mpa for 120 min tofinally obtain a double-sided copper clad laminate of 1.2 mm inthickness. A flame retardance of the laminate thus obtained wasevaluated according to the UL-94V standard. A soldering heat resistanceand a peel strength were measured in conformity with JIS C 6481, whereina soldering heat resistance was evaluated by inspecting whether or notappearance abnormality occurs after moisture absorption of a test piecekept in boiling water for 2 hours and in addition, immersion in a solderbath at 260 ° C. for 120 sec. Compounding recipes and results are shownin Table 1.

Examples 2 to 5 and Comparative Example 1

[0182] Double-sided copper clad laminates were fabricated in a methodsimilar to that used in Example 1 except for adoption of the recipesshown in Table 1. From the evaluation results shown in Table 1, it isfound that the laminates of compounding recipes shown in respectiveexamples are all excellent in flame retardance and moisture resistance.TABLE 1 compara- tive example example example example example example 12 3 4 5 1 phenol novolak resin 100 100 100 50 50 100 phosphazene 63compound A phosphazene 67 compound B phosphazene 146 compound Dphosphazene 50 compound E phosphazene 50 compound F phosphazene 70compound K phenol resin 45 44 triphenylphos-phine 0.2 0.2 0.2 0.2 0.20.2 phosphorus content 4.8 4.8 6.7 3.4 3.3 5.5 (%) nitrogen content (%)2.2 2.1 3 1.5 1.5 2.5 UL-94V V-0 V-0 V-0 V-0 V-0 V-0 soldering heat notnot not not not peeled resistance anoma- anoma- anoma- anoma- anoma-lous lous lous lous lous peel strength (kN/m) 1.79 1.75 1.83 1.83 1.821.05

Example 6

[0183] An epoxy resin composition of the present invention was producedin a procedure in which 12% by weight of a phosphazene compound (D)obtained in Synthesis Example 5, 72% by weight of fused silica powder,0.5% by weight of ester wax and 0.5% by weight of a silane couplingagent were added to 15% by weight of cresol novolak epoxy resin (with anepoxy equivalent of 215), all the components were mixed at ordinarytemperature and furthermore kneaded at a temperature from 90 to 95° C.,followed by cooling and obtained hard blocks were pulverized.

[0184] The epoxy resin composition is transfer injected into a metalmold heated at 170° C. and hardened therein to fabricate a moldedarticle (an encapsulated article). A water absorption, a glasstransition temperature and moisture resistance were measured on themolded article and test methods therefor are as follows:

[0185] Water Absorption (wt %): an epoxy resin composition of thepresent invention was transfer molded to produce a test piece of 50 mmin diameter and 3 mm in thickness, the test piece was stored in asaturated water vapor atmosphere at 127° C. under 2 atm for 24 hours anda water absorption was calculated from a change in weight of the testpiece.

[0186] Glass Transition Temperature (°C.): a test piece same as the testpiece for a water absorption test was post-cured (at 175° C. for 8hours) and thereafter, the test piece were subjected to measurement of aglass transition temperature with a thermal analyzer.

[0187] Moisture Resistance (PCT after immersion in a solder bath): Asilicon chip (a test element) having two or more aluminum wires thereonwas adhered to a 42 alloy frame by using an epoxy resin composition ofthe present invention and the chip was processed into a flat packagemolded article of 5×10×1.5 (mm) in size by transfer molding at 175° C.for 2 min. The intermediate molded article was post cured at 175° C. for8 hours, followed by a moisture resistance test on the test piece. Thatis, the flat package molded article was subjected firstly to moistureabsorption by storing in an atmosphere at 40° C. and 90% RH for 100hours in advance, secondly to an immersion treatment in a solder bath at250° C. for 10 sec, then PCT was performed on the article in a saturatedwater vapor atmosphere at 127° C. under 2.5 atm and if wiredisconnection due to corrosion of aluminum occurs on the article in thePCT, the article was evaluated as defective. A relationship between anelapsed time and a frequency of defective occurrence in PCT wasinvestigated. The number of samples was 20.

Comparative Example 2

[0188] Molded articles (encapsulated articles) were fabricated toevaluate properties such as moisture resistance and others in a similarmanner to Example 6 except for use of a phosphazene compound (K)obtained in Synthesis Example 8 instead of a phosphazene compound (D).Results are shown in Table 2. TABLE 2 example 6 comparative example 2water absorption (%) 0.03 0.49 glass transition 169 161 temperature (°C.) moisture resistance after 0/20 4/20 40 hours elapses after 100 hourselapses 0/20 12/20 after 150 hours elapses 0/20 20/20 after 200 hourselapses 0/20 —

[0189] In Example 6 of the present invention, wherein phosphazenecompounds having an amino group, a hydroxy group and a glycidyl groupwere used, a hot-state hardness was increased, water absorption was low,an adhesion strength and high temperature storage characteristics wereimproved as compared with Comparative Example 2 containing aphenoxyphosphazene compound. In the examples wherein a flame retardantof the present invention was used, molded articles were excellent in notonly high temperature storage characteristics but also flame retardance.

Reference Example 1

[0190] Fifteen parts of a phosphazene compound (G) of Synthetic Example9 and 0.5 part of PTFE were added to a resin composed of 70 parts byweight of aromatic polycarbonate resin and 30 parts by weight of ABSresin and the components were mixed in a mixer and thereafter, fused andkneaded using a 25 mm two-roll kneader to obtain a flame-retardant resincomposition.

[0191] The composition was prepared into a test piece of {fraction(1/16)} inch in thickness by means of injection molding and the testpieces was subjected to evaluation on flame retardance on the basis ofthe test method of UL-94, measurement on a thermal deformationtemperature in conformity with ASTM D-648 and further juicing and molddeposit (MD) phenomena were observed in molding.

Reference Examples 2 to 4

[0192] Phosphazene compounds (H) to (J) of Synthetic Examples 10 to 12were used instead of a phosphazene compound (G) of Synthetic Example 9and preparation of test pieces and evaluation thereof were performed ina similar way to Reference Example 1. Results are shown in Table 3.

Reference Comparative Example 1

[0193] A phenoxyphosphazene compound (K) of Synthetic Example 8 was usedinstead of a phosphazene compound (G) of Synthetic Example 9 andpreparation of test pieces and evaluation thereof were performed in asimilar way to Reference Example 1. Results are shown in Table 3.

Reference Example 5

[0194] Twenty five parts of a phosphazene polymer (G) produced inSynthetic Example 9 were added to 100 parts of ABS resin and thecomponents were mixed in a mixer and thereafter, fused and kneaded usinga 25 mm two-roll kneader to obtain a flame-retardant resin composition.

[0195] The composition was prepared into a test piece of {fraction(1/16)} inch in thickness by means of injection molding and the testpieces were subjected to evaluation on flame retardance on the basis ofthe test method of UL-94 and measurement on a thermal deformationtemperature in conformity with ASTM D-648 and furthermore, juicing andmold deposit (MD) phenomena were observed in molding. Results are shownin Table 3.

Reference Examples 6 to 8

[0196] Phosphazene compounds (H) to (J) of Synthetic Examples 10 to 12were used instead of a phosphazene compound (G) produced in SyntheticExample 9 and preparation of test pieces and evaluation thereof wereperformed in a similar way to Reference Example 5. Results are shown inTable 3.

Reference Comparative Example 2

[0197] A phenoxyphosphazene compound (K) produced in Synthesis Example 8was used instead of a phosphazene compound (G) produced in SyntheticExample 9 and preparation of test pieces and evaluation thereof wereperformed in a similar way to Reference Example 5. Results are shown inTable 3. Note that the term “Comparative Example” in the tables is anabbreviation of the term “Reference Comparative Example.” TABLE 3thermal deform- ation flame PTFE temper- juicing synthe- retard- part byature in tic resin ant weight UL-94V (° C.) molding MD reference PC/ABSG 0.5 V-0 109 absent absent example 1 reference PC/ABS H 0.5 V-0 106absent absent example 2 reference PC/ABS I 0.5 V-0 108 absent absentexample 3 reference PC/ABS J 0.5 V-0 106 absent absent example 4reference ABS G 0.5 V-0 82 absent absent example 5 reference ABS H 0.5V-0 83 absent absent example 6 reference ABS I 0.5 V-0 81 absent absentexample 7 reference ABS J 0.5 V-0 83 absent absent example 8 ComparativePC/ABS K 0.5 V-0 98 present present example 1 comparative ABS K 0.5 V-078 present present example 2

[0198] In such way, Reference Examples 1 to 8 using phosphazenecompounds of the present invention, thermal deformation temperature wasraised, neither of juicing and mold deposit phenomena was recognized ascompared with Reference Comparative Examples 1 and 2 containingphenoxyphosphazenes. In all of the examples using flame retardants ofthe present invention, any of vaporization, disappearance and bleedingout was not observed and in addition they are excellent in flameretardance.

[0199] A flame-retardant epoxy resin composition of the presentinvention was excellent in heat resistance and moisture resistance.

[0200] Therefore, a molded article obtained by molding a flame-retardantepoxy resin composition of the present invention has such excellentcharacteristics and is useful for various types of products.

[0201] Furthermore, electronic parts such as printed circuit substrateusing a flame-retardant epoxy resin composition of the present inventionwere excellent in heat resistance and moisture resistance and,consequently, have high usefulness in industrial aspects.

What is claimed is:
 1. A flame-retardant epoxy resin compositioncomprising an epoxy resin (A) and a phosphazene compound (B), whereinsaid phosphazene compound (B) is included in the range of 0.01 to 70% byweight relative to a total quantity of said epoxy resin (A) and saidphosphazene compound (B), and wherein said phosphazene compound (B) isat least one member selected from the group consisting of (1) a cyclicand/or a chain phosphazene compound expressed by a general formula

wherein each R¹ and R², being the same or different from each other, isan alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, analkylaryl group having 7 to 18 carbon atoms, an alkenyl group having 2to 18 carbon atoms, an alkenylaryl group having 8 to 18 carbon atoms, anamino group-substituted phenyl group, an aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, ahydroxy group-substituted phenyl group, a hydroxyalkyl group-substitutedphenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, aglycidyloxy group-substituted phenyl group or, a glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms, providing that at least one of n R¹s and n R²s is theamino group-substituted phenyl group, the aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, thehydroxyalkyl group-substituted phenyl group where the hydroxyalkyl grouphas 1 to 6 carbon atoms, the glycidyloxy group-substituted phenyl groupor the glycidyloxyalkyl group-substituted phenyl group where theglycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates aninteger of from 3 to 10000; (2) a polymer of said cyclic and/or saidchain phosphazene compound; and (3) a reaction product of said cyclicand/or said chain phosphazene compound with at least one compoundselected from the group consisting of an epoxy compound, a phenolcompound, an amine compound and an acid anhydride.
 2. Theflame-retardant epoxy resin composition according to claim 1, furthercomprising an epoxy hardener (C), wherein said phosphazene compound (B)and said epoxy hardener (C) are included in the range of 0.01 to 70% byweight and in the range of 0 to 70% by weight, respectively, relative toa total quantity of said epoxy resin (A), said phosphazene compound (B)and said epoxy hardener (C).
 3. A flame-retardant epoxy resincomposition comprising an epoxy resin (A), a phosphazene compound (B),an epoxy hardener (C) and an inorganic filler (D), wherein saidphosphazene compound (B) and said epoxy hardener (C) are included in therange of 0.01 to 70% by weight and in the range of 0 to 70% by weight,respectively, relative to a total quantity of said epoxy resin (A), saidphosphazene compound (B) and said epoxy hardener (C), and said inorganicfiller (D) is included in the range of 0 to 95% by weight relative to atotal quantity of said epoxy resin (A), said phosphazene compound (B),said epoxy hardener (C) and said inorganic filler (D) and wherein saidcomponent (B) is at least one member selected from the group consistingof (1) a cyclic and/or a chain phosphazene compound expressed by ageneral formula

wherein each R¹ and R², being the same as or different from each other,is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, analkylaryl group having 7 to 18 carbon atoms, an alkenyl group having 2to 18 carbon atoms, an alkenylaryl group having 8 to 18 carbon atoms, anamino group-substituted phenyl group, an aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, ahydroxy group-substituted phenyl group, a hydroxyalkyl group-substitutedphenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, aglycidyloxy group-substituted phenyl group or a glycidyloxyalkylgroup-substituted phenyl group where the glycidyloxyalkyl group has 4 to9 carbon atoms, providing that at least one of n R¹s and n R²s is theamino group-substituted phenyl group, the aminoalkyl group-substitutedphenyl group where the aminoalkyl group has 1 to 6 carbon atoms, thehydroxyalkyl group-substituted phenyl group where the hydroxyalkyl grouphas 1 to 6 carbon atoms, the glycidyloxy group-substituted phenyl groupor the glycidyloxyalkyl group-substituted phenyl group where theglycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates aninteger of from 3 to 10000; (2) a polymer of said cyclic and/or saidchain phosphazene compound; and (3) a reaction product of said cyclicand/or said chain phosphazene compound with at least one compoundselected from the group consisting of an epoxy compound, a phenolcompound, an amine compound and an acid anhydride.
 4. A molded articleobtained by molding the flame-retardant epoxy resin compositionaccording to any one of claims 1 to
 3. 5. An electronic part obtained bymolding the flame-retardant epoxy resin composition according to any oneof claims 1 to 3.